Effect of surface treatments and coffee thermocycling on the color and translucency of CAD-CAM monolithic glass-ceramic.

PubMed

Alp, Gulce; Subasi, Meryem Gulce; Johnston, William M; Yilmaz, Burak

2018-03-15

The effects of surface treatments and coffee thermocycling on the color and relative translucency of a recently introduced computer-aided design and computer-aided manufacturing (CAD-CAM) monolithic glass-ceramic are unknown. The purpose of this in vitro study was to evaluate the effect of coffee thermocycling on the color and relative translucency parameter (RTP) of CAD-CAM monolithic glass-ceramics after different surface treatments. Specimens (1.5-mm-thick) were sectioned from zirconia-reinforced lithium silicate glass-ceramic (ZLS) (n=18) and lithium disilicate glass-ceramic (LDS) blocks (n=18). Two different types of surface treatments (glazing or polishing) were applied to the specimens. The specimens were subjected to 5000 thermocycles in a coffee solution. The color coordinates of specimens were measured before and after coffee thermocycling by using a spectroradiometer, and color differences and relative translucency values were calculated by using CIEDE2000 color difference and RTP formulas. ANOVA was used to analyze the color difference and relative translucency values by using maximum likelihood estimation and the Satterthwaite degrees of freedom methods. Any significant interaction between surface subgroups was further analyzed by using the Tukey-Kramer adjustment (α=.05). Material type had a significant effect on color difference (P=.018). All color difference values of all materials were smaller than the clinical acceptability threshold (<1.8 units). For relative translucency, material (P<.001) and coffee thermocycling had a significant effect (P=.014), and an interaction was found between the surface treatments and materials (P<.001). The Tukey-Kramer test revealed significant differences between glazed and polished subgroups of LDS material, except for ZLS-glazed and ZLS-polished subgroups. Different surface treatments of CAD-CAM monolithic zirconia-reinforced lithium silicate and lithium disilicate glass-ceramics resulted in clinically acceptable color changes after coffee thermocycling. The color changes in all groups, except for LDS-polished, were not perceivable. Lithium disilicate was more translucent than zirconia-reinforced lithium silicate before and after coffee thermocycling. Coffee thermocycling decreased the translucency of both of the materials. Different surface treatments affected the translucency of only lithium disilicate for tested thickness. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Fracture strength of lithium disilicate crowns compared to polymer-infiltrated ceramic-network and zirconia reinforced lithium silicate crowns.

PubMed

Sieper, Kim; Wille, Sebastian; Kern, Matthias

2017-10-01

The aim of this study was to evaluate the fracture strength of crowns made from current CAD/CAM materials. In addition the influence of crown thickness and chewing simulation on the fracture strength was evaluated. Crowns were fabricated from lithium disilicate, zirconia reinforced lithium silicate (ZLS-ceramic) and a polymer-infiltrated ceramic-network (PICN) with an occlusal thickness of 1.0mm or 1.5mm, respectively (n=16). Crowns were cemented on composite dies. Subgroups of eight specimens were loaded with 5kg in a chewing simulator for 1,200,000 cycles with thermal cycling. Finally, all specimens were loaded until fracture in a universal testing machine. Three-way ANOVA was used to detect statistical interaction. Differences regarding the materials were tested with two-way ANOVA, following one-way ANOVA and a post-hoc Tukey's-Test. All crowns survived the chewing simulation. The material had a significant influence on the fracture resistance (p≤0.05). Lithium disilicate achieved the highest values of fracture strength in almost all groups followed by ZLS-ceramic. PICN achieved the lowest values of fracture strength. Chewing simulation increased the fracture strength of thick lithium disilicate crown significantly. Greater occlusal thickness of all crown materials resulted in higher crown fracture strength before chewing simulation. After chewing simulation occlusal thickness of lithium disilicate and PICN crowns had no significant influence on the fracture strength. All crowns revealed fracture strength above the clinically expected loading forces. Therefore the durability of the tested CAD/CAM materials seems promising also in an occlusal thickness of 1.0mm. Copyright © 2017 Elsevier Ltd. All rights reserved.

Digital evaluation of the fit of zirconia-reinforced lithium silicate crowns with a new three-dimensional approach.

PubMed

Zimmermann, Moritz; Valcanaia, Andre; Neiva, Gisele; Mehl, Albert; Fasbinder, Dennis

2017-11-30

Several methods for the evaluation of fit of computer-aided design/computer-assisted manufacture (CAD/CAM)-fabricated restorations have been described. In the study, digital models were recorded with an intraoral scanning device and were measured using a new three-dimensional (3D) computer technique to evaluate restoration internal fit. The aim of the study was to evaluate the internal adaptation and fit of chairside CAD/CAM-fabricated zirconia-reinforced lithium silicate ceramic crowns fabricated with different post-milling protocols. The null hypothesis was that different post-milling protocols did not influence the fitting accuracy of zirconia-reinforced lithium silicate restorations. A master all-ceramic crown preparation was completed on a maxillary right first molar on a typodont. Twenty zirconia-reinforced lithium silicate ceramic crowns (Celtra Duo, Dentsply Sirona) were designed and milled using a chairside CAD/CAM system (CEREC Omnicam, Dentsply Sirona). The 20 crowns were randomly divided into two groups based on post-milling protocols: no manipulation after milling (Group MI) and oven fired-glazing after milling (Group FG). A 3D computer method was used to evaluate the internal adaptation of the crowns. This was based on a subtractive analysis of a digital scan of the crown preparation and a digital scan of the thickness of the cement space over the crown preparation as recorded by a polyvinylsiloxane (PVS) impression material. The preparation scan and PVS scan were matched in 3D and a 3D difference analysis was performed with a software program (OraCheck, Cyfex). Three areas of internal adaptation and fit were selected for analysis: margin (MA), axial wall (AX), and occlusal surface (OC). Statistical analysis was performed using 80% percentile and one-way ANOVA with post-hoc Scheffé test (P = .05). The closest internal adaptation of the crowns was measured at the axial wall with 102.0 ± 11.7 µm for group MI-AX and 106.3 ± 29.3 µm for group FG-AX. The largest internal adaptation of the crowns was measured for the occlusal surface with 258.9 ± 39.2 µm for group MI-OC and 260.6 ± 55.0 µm for group FG-OC. No statistically significant differences were found for the post-milling protocols (P > .05). The 3D difference pattern was visually analyzed for each area with a color-coded scheme. Post-milling processing did not affect the internal adaptation of zirconia-reinforced lithium silicate crowns fabricated with a chairside CAD/CAM technique. The new 3D computer technique for the evaluation of fit of restorations may be highly promising and has the opportunity to be applied to clinical studies.

Copper Silicate Hydrate Hollow Spheres Constructed by Nanotubes Encapsulated in Reduced Graphene Oxide as Long-Life Lithium-Ion Battery Anode.

PubMed

Wei, Xiujuan; Tang, Chunjuan; Wang, Xuanpeng; Zhou, Liang; Wei, Qiulong; Yan, Mengyu; Sheng, Jinzhi; Hu, Ping; Wang, Bolun; Mai, Liqiang

2015-12-09

Hierarchical copper silicate hydrate hollow spheres-reduced graphene oxide (RGO) composite is successfully fabricated by a facile hydrothermal method using silica as in situ sacrificing template. The electrochemical performance of the composite as lithium-ion battery anode was studied for the first time. Benefiting from the synergistic effect of the hierarchical hollow structure and conductive RGO matrix, the composite exhibits excellent long-life performance and rate capability. A capacity of 890 mAh/g is achieved after 200 cycles at 200 mA/g and a capacity of 429 mAh/g is retained after 800 cycles at 1000 mA/g. The results indicate that the strategy of combining hierarchical hollow structures with conductive RGO holds the potential in addressing the volume expansion issue of high capacity anode materials.

Pulse energy dependence of refractive index change in lithium niobium silicate glass during femtosecond laser direct writing.

PubMed

Cao, Jing; Poumellec, Bertrand; Brisset, François; Lancry, Matthieu

2018-03-19

Femtosecond laser-induced refractive index changes in lithium niobium silicate glass were explored at high repetition rate (300 fs, 500 kHz) by polarized light microscopy, full-wave retardation plate, quantitative birefringence microscopy, and digital holographic microscopy. We found three regimes on energy increase. The first one corresponds to isotropic negative refractive index change (for pulse energy ranging 0.4-0.8 μJ/pulse, 0.6 NA, 5μm/s, 650μm focusing depth in the glass). The second one (0.8-1.2 μJ/pulse) corresponds to birefringence with well-defined slow axis orientation. The third one (above 1.2 μJ/pulse) is related to birefringence direction fluctuation. Interestingly, these regimes are consistent with crystallization ones. In addition, an asymmetric orientational writing effect has been detected on birefringence. These topics extend the possibility of controlling refractive index change in multi-component glasses.

Dispersion and thermal properties of lithium aluminum silicate glasses doped with Cr3+ ions

NASA Astrophysics Data System (ADS)

El-Diasty, Fouad; Abdel-Baki, Manal; Abdel Wahab, Fathy A.; Darwish, Hussein

2006-10-01

A series of new lithium aluminum silicate (LAS) glass systems doped with chromium ion is prepared. The reflectance and transmittance of the glass slabs are recorded. By means of an iteration procedure, the glass refractive index n and the extinction coefficient k and their dispersions are obtained. Across a wide spectral range of 0.2-1.6 μm, the dispersion curves are used to determine the atomic and quantum constants of the prepared glasses. These findings provide the average oscillator wavelength, the average oscillator strength, oscillator energy, dispersion energy, lattice energy, and material dispersion of the glass materials to be calculated. For optical waveguide applications, the wavelength for zero material dispersion is obtained. Dilatometric measurements are performed and the thermal expansion coefficient is calculated to throw some light on the thermo-optical properties of the present glasses correlating them with their structure and the presence of nonbridging oxygen ions.

High-temperature ultrasonic characterization of the mechanical and microstructural behavior of a fibrous composite with a magnesium lithium aluminum silicate glass-ceramic matrix

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cutard, T.; Huger, M.; Fargeot, D.

The mechanical behavior and the microstructural modifications of a SiC-fiber-reinforced magnesium lithium aluminum silicate glass-ceramic (SiC/MASL) have been characterized by ultrasonic measurement of uniaxial Young`s modulus at high temperature. Under vacuum, long isothermal agings in the 750--1,000 C temperature range have shown matrix modifications in terms of crystallization of residual glassy phases, and of phase transformations in the Li{sub 2}O-Al{sub 2}O{sub 3}-SiO{sub 2} system. In air, long isothermal agings performed under the same conditions have led to the same matrix transformations but in competition with oxidation mechanisms of the carbon fiber-matrix interphase. All of these matrix and/or interface transformations havemore » been confirmed by X-ray diffraction analysis, scanning electron microscopy, scanning acoustic microscopy, and microindentation tests.« less

Comment on "Rapid cooling and cold storage in a silicic magma reservoir recorded in individual crystals".

PubMed

Wilson, Colin J N; Morgan, Daniel J; Charlier, Bruce L A; Barker, Simon J

2017-12-22

Rubin et al (Reports, 16 June 2017, p. 1154) proposed that gradients in lithium abundance in zircons from a rhyolitic eruption in New Zealand reflected short-lived residence at magmatic temperatures interleaved with long-term "cold" (<650°C) storage. Important issues arise with the interpretation of these lithium gradients and consequent crystal thermal histories that raise concerns about the validity of this conclusion. Copyright © 2017, American Association for the Advancement of Science.

Continental erosion and the Cenozoic rise of marine diatoms

NASA Astrophysics Data System (ADS)

Cermeño, Pedro; Falkowski, Paul G.; Romero, Oscar E.; Schaller, Morgan F.; Vallina, Sergio M.

2015-04-01

Marine diatoms are silica-precipitating microalgae that account for over half of organic carbon burial in marine sediments and thus they play a key role in the global carbon cycle. Their evolutionary expansion during the Cenozoic era (66 Ma to present) has been associated with a superior competitive ability for silicic acid relative to other siliceous plankton such as radiolarians, which evolved by reducing the weight of their silica test. Here we use a mathematical model in which diatoms and radiolarians compete for silicic acid to show that the observed reduction in the weight of radiolarian tests is insufficient to explain the rise of diatoms. Using the lithium isotope record of seawater as a proxy of silicate rock weathering and erosion, we calculate changes in the input flux of silicic acid to the oceans. Our results indicate that the long-term massive erosion of continental silicates was critical to the subsequent success of diatoms in marine ecosystems over the last 40 My and suggest an increase in the strength and efficiency of the oceanic biological pump over this period.

Continental erosion and the Cenozoic rise of marine diatoms

PubMed Central

Cermeño, Pedro; Falkowski, Paul G.; Romero, Oscar E.; Schaller, Morgan F.; Vallina, Sergio M.

2015-01-01

Marine diatoms are silica-precipitating microalgae that account for over half of organic carbon burial in marine sediments and thus they play a key role in the global carbon cycle. Their evolutionary expansion during the Cenozoic era (66 Ma to present) has been associated with a superior competitive ability for silicic acid relative to other siliceous plankton such as radiolarians, which evolved by reducing the weight of their silica test. Here we use a mathematical model in which diatoms and radiolarians compete for silicic acid to show that the observed reduction in the weight of radiolarian tests is insufficient to explain the rise of diatoms. Using the lithium isotope record of seawater as a proxy of silicate rock weathering and erosion, we calculate changes in the input flux of silicic acid to the oceans. Our results indicate that the long-term massive erosion of continental silicates was critical to the subsequent success of diatoms in marine ecosystems over the last 40 My and suggest an increase in the strength and efficiency of the oceanic biological pump over this period. PMID:25831504

Continental erosion and the Cenozoic rise of marine diatoms.

PubMed

Cermeño, Pedro; Falkowski, Paul G; Romero, Oscar E; Schaller, Morgan F; Vallina, Sergio M

2015-04-07

Marine diatoms are silica-precipitating microalgae that account for over half of organic carbon burial in marine sediments and thus they play a key role in the global carbon cycle. Their evolutionary expansion during the Cenozoic era (66 Ma to present) has been associated with a superior competitive ability for silicic acid relative to other siliceous plankton such as radiolarians, which evolved by reducing the weight of their silica test. Here we use a mathematical model in which diatoms and radiolarians compete for silicic acid to show that the observed reduction in the weight of radiolarian tests is insufficient to explain the rise of diatoms. Using the lithium isotope record of seawater as a proxy of silicate rock weathering and erosion, we calculate changes in the input flux of silicic acid to the oceans. Our results indicate that the long-term massive erosion of continental silicates was critical to the subsequent success of diatoms in marine ecosystems over the last 40 My and suggest an increase in the strength and efficiency of the oceanic biological pump over this period.

MAS-NMR studies of lithium aluminum silicate (LAS) glasses and glass-ceramics having different Li 2O/Al 2O 3 ratio

NASA Astrophysics Data System (ADS)

Ananthanarayanan, A.; Kothiyal, G. P.; Montagne, L.; Revel, B.

2010-01-01

Emergence of phases in lithium aluminum silicate (LAS) glasses of composition (wt%) xLi 2O-71.7SiO 2-(17.7- x)Al 2O 3-4.9K 2O-3.2B 2O 3-2.5P 2O 5 (5.1≤ x≤12.6) upon heat treatment were studied. 29Si, 27Al, 31P and 11B MAS-NMR were employed for structural characterization of both LAS glasses and glass-ceramics. In glass samples, Al is found in tetrahedral coordination, while P exists mainly in the form of orthophosphate units. B exists as BO 3 and BO 4 units. 27Al NMR spectra show no change with crystallization, ruling out the presence of any Al containing phase. Contrary to X-ray diffraction studies carried out, 11B (high field 18.8 T) and 29Si NMR spectra clearly indicate the unexpected crystallization of a borosilicate phase (Li,K)BSi 2O 6, whose structure is similar to the aluminosilicate virgilite. Also, lithium disilicate (Li 2Si 2O 5), lithium metasilicate (Li 2SiO 3) and quartz (SiO 2) were identified in the 29Si NMR spectra of the glass-ceramics. 31P NMR spectra of the glass-ceramics revealed the presence of Li 3PO 4 and a mixed phase (Li,K) 3PO 4 at low alkali concentrations.

The effects of lithium hydroxide solution on alkali silica reaction gels created with opal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitchell, Lyndon D.; Beaudoin, James J.; Grattan-Bellew, Patrick

The reaction of Nevada opal with calcium hydroxide, potassium hydroxide and lithium hydroxide solutions was investigated. In addition, opal was exposed to a combined solution of these three hydroxides. The progress of the three reactions was followed using X-ray diffraction (XRD), {sup 29}Si nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). The XRD results indicated the presence of a low-angle peak exclusive to the lithium-based reactions. The NMR results suggested a change in the silicate structure in the presence of lithium. These techniques indicated that the reaction of the alkali with the opal starting material is inhibited and perhapsmore » stopped in the presence of lithium hydroxide. SEM revealed that the morphology of the reaction products on the surface of the reacted opal grains is markedly different invariably. It was concluded that evidence to support the theory of a protective layer exists and that the nature of the layer varies with ion type.« less

Extended glaze firing on ceramics for hard machining: Crack healing, residual stresses, optical and microstructural aspects.

PubMed

Aurélio, Iana L; Dorneles, Lucio S; May, Liliana G

2017-02-01

To evaluate the effect of extended and conventional (manufacturer-recommended) glaze firings on crack healing, residual stresses, optical characteristics and crystalline structure of four ceramics for hard machining. Rectangular specimens were obtained by sectioning densely sintered feldspathic (FEL), leucite- (LEU), lithium disilicate- (DIS), and zirconia-reinforced lithium silicate-based (ZLS) prefabricated ceramic blocks and divided into groups according to the applied glaze firing (n=5): conventional glaze/manufacturer-recommended (G), extended glaze (EG) and control/no heat treatment (C). Defects generated by indentation were analyzed by scanning electron microscopy before and after firing (n=1) to evaluate crack healing. Residual stresses were determined by the indentation technique. Color differences (ΔE) after firing were measured by CIEDE2000 formula, and translucency variations were quantified by contrast ratio. Stability of crystalline microstructure was analyzed by X-ray diffraction. Regardless of the material, EG had greater ability than G to heal defects, and produced compressive residual stresses, while G generated tensile stresses. Color differences produced by EG were: imperceptible for FEL and LEU ceramics; perceptible, but still clinically acceptable for DIS; clinically unacceptable for ZLS. G produced no perceptible color change. The DIS and ZLS ceramics became ≈1% more opaque after G, ≈4% and ≈15%, respectively, after EG. The crystalline phase of all the ceramics remained stable after G and EG. Extended glaze firing could be an alternative to finish feldspathic, leucite-, and lithium disilicate-based ceramic restorations, since it provides greater crack healing than the conventional glaze firing. It develops tolerable residual stresses, and produces clinically acceptable color alterations, without altering the microstructure of these materials. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Femtosecond laser-induced refractive index modification in multicomponent glasses

NASA Astrophysics Data System (ADS)

Bhardwaj, V. R.; Simova, E.; Corkum, P. B.; Rayner, D. M.; Hnatovsky, C.; Taylor, R. S.; Schreder, B.; Kluge, M.; Zimmer, J.

2005-04-01

We present a comprehensive study on femtosecond laser-induced refractive index modification in a wide variety of multicomponent glasses grouped as borosilicate, aluminum-silicate, and heavy-metal oxide glasses along with lanthanum-borate and sodium-phosphate glasses. By using high-spatial resolution refractive index profiling techniques, we demonstrate that under a wide range of writing conditions the refractive index modification in multicomponent glasses can be positive, negative, or nonuniform, and exhibits a strong dependence on the glass composition. With the exception of some aluminum-silicate glasses all other glasses exhibited a negative/nonuniform index change. We also demonstrate direct writing of waveguides in photosensitive Foturan® glass with a femtosecond laser without initiating crystallization by thermal treatment. Upon ceramization of lithium-aluminum-silicate glasses such as Foturan®, Zerodur®, and Robax® we observe switching of laser-induced refractive index change from being positive to negative. The measured transmission losses in the waveguides at 1550nm agree with the index profile measurements in alkali-free aluminum-silicate glasses.

Lithium conductivity in glasses of the Li2O-Al2O3-SiO2 system.

PubMed

Ross, Sebastian; Welsch, Anna-Maria; Behrens, Harald

2015-01-07

To improve the understanding of Li-dynamics in oxide glasses, i.e. the effect of [AlO4](-) tetrahedra and non-bridging oxygens on the potential landscape, electrical conductivity of seven fully polymerized and partly depolymerized lithium aluminosilicate glasses was investigated using impedance spectroscopy (IS). Lithium is the only mobile particle in these materials. Data derived from IS, i.e. activation energies, pre-exponential factors and diffusivities for lithium, are interpreted in light of Raman spectroscopic analyses of local structures in order to identify building units, which are crucial for lithium dynamics and migration. In polymerized glasses (compositional join LiAlSiO4-LiAlSi4O10) the direct current (DC) electrical conductivity continuously increases with increasing lithium content while lithium diffusivity is not affected by the Al/Si ratio in the glasses. Hence, the increase in electrical conductivity can be solely assigned to lithium concentration in the glasses. An excess of Li with respect to Al, i.e. the introduction of non-bridging oxygen into the network, causes a decrease in lithium mobility in the glasses. Activation energies in polymerized glasses (66 to 70 kJ mol(-1)) are significantly lower than those in depolymerized networks (76 to 78 kJ mol(-1)) while pre-exponential factors are nearly constant across all compositions. Comparison of the data with results for lithium silicates from the literature indicates a minimum in lithium diffusivity for glasses containing both aluminium tetrahedra and non-bridging oxygens. The findings allow a prediction of DC conductivity for a large variety of lithium aluminosilicate glass compositions.

Preparation and physicochemical properties of surfactant-free emulsions using electrolytic-reduction ion water containing lithium magnesium sodium silicate.

PubMed

Okajima, Masahiro; Wada, Yuko; Hosoya, Takashi; Hino, Fumio; Kitahara, Yoshiyasu; Shimokawa, Ken-ichi; Ishii, Fumiyoshi

2013-04-01

Surfactant-free emulsions by adding jojoba oil, squalane, olive oil, or glyceryl trioctanoate (medium chain fatty acid triglycerides, MCT) to electrolytic-reduction ion water containing lithium magnesium sodium silicate (GE-100) were prepared, and their physiochemical properties (thixotropy, zeta potential, and mean particle diameter) were evaluated. At an oil concentration of 10%, the zeta potential was ‒22.3 ‒ ‒26.8 mV, showing no marked differences among the emulsions of various types of oil, but the mean particle diameters in the olive oil emulsion (327 nm) and MCT emulsion (295 nm) were smaller than those in the other oil emulsions (452-471 nm). In addition, measurement of the hysteresis loop area of each type of emulsion revealed extremely high thixotropy of the emulsion containing MCT at a low concentration and the olive emulsion. Based on these results, since surfactants and antiseptic agents markedly damage sensitive skin tissue such as that with atopic dermatitis, surfactant- and antiseptic-free emulsions are expected to be new bases for drugs for external use.

Influence of Different CAM Strategies on the Fit of Partial Crown Restorations: A Digital Three-dimensional Evaluation.

PubMed

Zimmermann, M; Valcanaia, A; Neiva, G; Mehl, A; Fasbinder, D

2018-04-09

CAM fabrication is an important step within the CAD/CAM process. The internal fit of restorations is influenced by the accuracy of the subtractive CAM procedure. Little is known about how CAM strategies might influence the fit of CAD/CAM fabricated restorations. The aim of this study was to three-dimensionally evaluate the fit of CAD/CAM fabricated zirconia-reinforced lithium silicate ceramic partial crowns fabricated with three different CAM strategies. The null hypothesis was that different CAM strategies did not influence the fitting accuracy of CAD/CAM fabricated zirconia-reinforced lithium silicate ceramic partial crowns. Preparation for a partial crown was performed on a maxillary right first molar on a typodont. A chairside CAD/CAM system with the intraoral scanning device CEREC Omnicam (Dentsply Sirona, York, PA, USA) and the 3+1 axis milling unit CEREC MCXL was used. There were three groups with different CAM strategies: step bur 12 (12), step bur 12S (12S), and two step-mode (12TWO). The zirconia-reinforced lithium silicate ceramic Celtra Duo (Dentsply Sirona) was used as the CAD/CAM material. A new 3D method for evaluating the fit was applied, consisting of the quadrant scan with the intraoral scanning device CEREC Omnicam. The scan of the PVS material adherent to the preparation and the preparation scan were matched, and the difference analysis was performed with special software OraCheck (Cyfex AG, Zurich, Switzerland). Three areas were selected for analysis: margin (MA), axial (AX), and occlusal (OC). Statistical analysis was performed using 80% percentile, one-way ANOVA, and the post hoc Scheffé test with α=0.05. Statistically significant differences were found both within and between the test groups. The aspect axial fit results varied from 90.5 ± 20.1 μm for the two-step milling mode (12TWO_AX) to 122.8 ± 12.2 μm for the milling with step bur 12S (12S_AX). The worst result in all groups was found for the aspect occlusal fit with the highest value for group 12S of 222.8 ± 35.6 μm. Group two-step milling mode (12TWO) performed statistically significantly better from groups 12 and 12S for the occlusal fit ( p<0.05). Deviation patterns were visually analyzed with a color-coded scheme for each restoration. CAM strategy influenced the internal adaptation of zirconia-reinforced lithium silicate partial crowns fabricated with a chairside CAD/CAM system. Sensible selection of specific areas of internal adaptation and fit is an important factor for evaluating the CAM accuracy of CAD/CAM systems.

XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

NASA Technical Reports Server (NTRS)

Fuss, T.; Mogus-Milankovic, A.; Ray, C. S.; Lesher, C. E.; Youngman, R.; Day, D. E.

2006-01-01

The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

Effect of Heat-Pressing Temperature and Holding Time on the Microstructure and Flexural Strength of Lithium Disilicate Glass-Ceramics

PubMed Central

Gao, Jing; Wang, Hui; Chen, Jihua

2015-01-01

The present study aimed to evaluate the influence of various heat-pressing procedures (different holding time and heat pressing temperature) on the microstructure and flexural strength of lithium disilicate glass ceramic. An experimental lithium silicate glass ceramic (ELDC) was prepared from the SiO2-Li2O-K2O-Al2O3-ZrO2-P2O5 system and heat-pressed following different procedures by varying temperature and holding time. The flexural strength was tested and microstructure was analyzed. The relationships between the microstructure, mechanical properties and heat-pressing procedures were discussed in-depth. Results verified the feasibility of the application of dental heat-pressing technique in processing the experimental lithium disilicate glass ceramic. Different heat-pressing procedures showed significant influence on microstructure and flexural strength. ELDC heat-pressed at 950℃ with holding time of 15 min achieved an almost pore-free microstructure and the highest flexural strength, which was suitable for dental restorative application. PMID:25985206

Ultrasonic Monitoring of the Interaction between Cement Matrix and Alkaline Silicate Solution in Self-Healing Systems.

PubMed

Ait Ouarabi, Mohand; Antonaci, Paola; Boubenider, Fouad; Gliozzi, Antonio S; Scalerandi, Marco

2017-01-07

Alkaline solutions, such as sodium, potassium or lithium silicates, appear to be very promising as healing agents for the development of encapsulated self-healing concretes. However, the evolution of their mechanical and acoustic properties in time has not yet been completely clarified, especially regarding their behavior and related kinetics when they are used in the form of a thin layer in contact with a hardened cement matrix. This study aims to monitor, using linear and nonlinear ultrasonic methods, the evolution of a sodium silicate solution interacting with a cement matrix in the presence of localized cracks. The ultrasonic inspection via linear methods revealed that an almost complete recovery of the elastic and acoustic properties occurred within a few days of healing. The nonlinear ultrasonic measurements contributed to provide further insight into the kinetics of the recovery due to the presence of the healing agent. A good regain of mechanical performance was ascertained through flexural tests at the end of the healing process, confirming the suitability of sodium silicate as a healing agent for self-healing cementitious systems.

Ultrastructural analysis of dental ceramic surface processed by a 1070 nm fiber laser

NASA Astrophysics Data System (ADS)

Fornaini, C.; Merigo, E.; Poli, F.; Rocca, J.-P.; Selleri, S.; Cucinotta, A.

2018-04-01

Background: Lithium di-silicate dental ceramic bonding, realized by using different resins, is strictly dependent on micro-mechanical retention and chemical adhesion. The aim of this in vitro study was to investigate the capability of a 1070 nm fibre laser for their surface treatment. Methods: Samples were irradiated by a pulsed fibre laser at 1070 nm with different parameters (peak power of 5, 7.5, and 10 kW, repetition rate (RR) 20 kHz, speed of 10 and 50 mm/sec, and total energy density from 1.3 to 27 kW/cm2) Subsequently, the surface modifications were analysed by optical microscope, scanning electron microscope (SEM) and energy dispersive X-ray Spectroscopy (EDS). Results: With a peak power of 5 kW, RR of 20 kHz, and speed of 50 mm/sec, the microscopic observation of the irradiated surface showed increased roughness with small areas of melting and carbonization. EDS analysis revealed that, with these parameters, there are no evident differences between laser-processed samples and controls. Conclusions: A 1070 nm fibre laser can be considered as a good device to increase the adhesion of lithium di-silicate ceramics when optimum parameters are considered.

Method of recycling lithium borate to lithium borohydride through diborane

DOEpatents

Filby, Evan E.

1976-01-01

This invention provides a method for the recycling of lithium borate to lithium borohydride which can be reacted with water to generate hydrogen for utilization as a fuel. The lithium borate by-product of the hydrogen generation reaction is reacted with hydrogen chloride and water to produce boric acid and lithium chloride. The boric acid and lithium chloride are converted to lithium borohydride through a diborane intermediate to complete the recycle scheme.

Method of recycling lithium borate to lithium borohydride through methyl borate

DOEpatents

Filby, Evan E.

1977-01-01

This invention provides a method for the recycling of lithium borate to lithium borohydride which can be reacted with water to generate hydrogen for utilization as a fuel. The lithium borate by-product of the hydrogen generation reaction is reacted with hydrogen chloride and water to produce boric acid and lithium chloride. The boric acid and lithium chloride are converted to lithium borohydride through a methyl borate intermediate to complete the recycle scheme.

Silicate melt inclusion evidence for extreme pre-eruptive enrichment and post-eruptive depletion of lithium in silicic volcanic rocks of the western United States: implications for the origin of lithium-rich brines

USGS Publications Warehouse

Hofstra, Albert H.; Todorov, T.I.; Mercer, C.N.; Adams, D.T.; Marsh, E.E.

2013-01-01

To evaluate whether anatectic and/or highly fractionated lithophile element-enriched rhyolite tuffs deposited in arid lacustrine basins lose enough lithium during eruption, lithification, and weathering to generate significant Li brine resources, pre-eruptive melt compositions, preserved in inclusions, and the magnitude of post-eruptive Li depletions, evident in host rhyolites, were documented at six sites in the western United States. Each rhyolite is a member of the bimodal basalt-rhyolite assemblage associated with extensional tectonics that produced the Basin and Range province and Rio Grande rift, an evolving pattern of closed drainage basins, and geothermal energy or mineral resources. Results from the 0.8 Ma Bishop tuff (geothermal) in California, 1.3 to 1.6 Ma Cerro Toledo and Upper Bandelier tephra (geothermal) and 27.9 Ma Taylor Creek rhyolite (Sn) in New Mexico, 21.7 Ma Spor Mountain tuff (Be, U, F) and 24.6 Ma Pine Grove tuff (Mo) in Utah, and 27.6 Ma Hideaway Park tuff (Mo) in Colorado support the following conclusions. Melt inclusions in quartz phenocrysts from rhyolite tuffs associated with hydrothermal deposits of Sn, Mo, and Be are extremely enriched in Li (1,000s of ppm); those from Spor Mountain have the highest Li abundance yet recorded (max 5,200 ppm, median 3,750 ppm). Forty-five to 98% of the Li present in pre-eruptive magma was lost to the environment from these rhyolite tuffs. The amount of Li lost from the small volumes (1–10 km3) of Li-enriched rhyolite deposited in closed basins is sufficient to produce world-class Li brine resources. After each eruption, meteoric water leaches Li from tuff, which drains into playas, where it is concentrated by evaporation. The localized occurrence of Li-enriched rhyolites may explain why brines in arid lacustrine basins seldom have economic concentrations of Li. Considering that hydrothermal deposits of Sn, Mo, Be, U, and F may indicate potential for Li brines in nearby basins, we surmise that the world’s largest Li brine resource in the Salar de Uyuni (10 Mt) received Li from nearby rhyolite tuffs in the Bolivian tin belt.

Li diffusion and the effect of local structure on Li mobility in Li2O-SiO2 glasses.

PubMed

Bauer, Ute; Welsch, Anna-Maria; Behrens, Harald; Rahn, Johanna; Schmidt, Harald; Horn, Ingo

2013-12-05

Aimed to improve the understanding of lithium migration mechanisms in ion conductors, this study focuses on Li dynamics in binary Li silicate glasses. Isotope exchange experiments and conductivity measurements were carried out to determine self-diffusion coefficients and activation energies for Li migration in Li2Si3O7 and Li2Si6O13 glasses. Samples of identical composition but different isotope content were combined for diffusion experiments in couples or triples. Diffusion profiles developed between 511 and 664 K were analyzed by femtosecond laser ablation combined with multiple collector inductively coupled plasma mass spectrometry (fs LA-MC-ICP-MS) and secondary ion mass spectrometry (SIMS). Analyses of diffusion profiles and comparison of diffusion data reveal that the isotope effect of lithium diffusion in silicate glasses is rather small, consistent with classical diffusion behavior. Ionic conductivity of glasses was measured between 312 and 675 K. The experimentally obtained self-diffusion coefficient, D(IE), and ionic diffusion coefficient, D(σ), derived from specific DC conductivity provided information about correlation effects during Li diffusion. The D(IE)/D(σ) is higher for the trisilicate (0.27 ± 0.05) than that for the hexasilicate (0.17 ± 0.02), implying that increasing silica content reduces the efficiency of Li jumps in terms of long-range movement. This trend can be rationalized by structural concepts based on nuclear magnetic resonance (NMR) and Raman spectroscopy as well as molecular dynamic simulations, that is, lithium is percolating in low-dimensional, alkali-rich regions separated by a silica-rich matrix.

Variety of neutron sensors based on scintillating glass waveguides

NASA Astrophysics Data System (ADS)

Bliss, Mary; Craig, Richard A.

1995-04-01

Pacific Northwest Laboratory (PNL) has fabricated cerium-activated lithium silicate glass scintillating fiber waveguide neutron sensors via a hot-downdraw process. These fibers typically have a transmission length (e-1 length) of greater than 2 meters. The underlying physics of, the properties of, and selected devices incorporating these fibers are described. These fibers constitute an enabling technology for a wide variety of neutron sensors.

Ceramic Life Prediction Methodology.

DTIC Science & Technology

1986-03-01

stress rupture data were collected on two materials, a sintered silicon nitride and a lithium-aluminum-silicate. The fast fracture data was presented...graphically in the form of Weibull plots of percent failed versus failure stress . The stress rupture results were presented in tabular form. Photo...micrographs were presented to illustrate the fracture surfaces of fast fracture and stress rupture failures. A program of specimen development was coaducted

Indirect zirconia-reinforced lithium silicate ceramic CAD/CAM restorations: Preliminary clinical results after 12 months.

PubMed

Zimmermann, Moritz; Koller, Christina; Mehl, Albert; Hickel, Reinhard

2017-01-01

No clinical data are available for the new computer-aided design/computer-assisted manufacture (CAD/CAM) material zirconia-reinforced lithium silicate (ZLS) ceramic. This study describes preliminary clinical results for indirect ZLS CAD/CAM restorations after 12 months. Indirect restorations were fabricated, using the CEREC method and intraoral scanning (CEREC Omnicam, CEREC MCXL). Sixty-seven restorations were seated adhesively (baseline). Sixty restorations were evaluated after 12 months (follow-up), using modified FDI criteria. Two groups were established, according to ZLS restorations' post-processing procedure prior to adhesive seating: group I (three-step polishing, n = 32) and group II (fire glazing, n = 28). Statistical analysis was performed with Mann-Whitney U test and Wilcoxon test (P < .05). The success rate of indirect ZLS CAD/CAM restorations after 12 months was 96.7%. Two restorations clinically failed as a result of bulk fracture (failure rate 3.3%). No statistically significant differences were found for baseline and follow-up criteria (Wilcoxon test, P > .05). Statistically significant differences were found for criteria surface gloss for group I and group II (Mann-Whitney U test, P < .05). This study demonstrates ZLS CAD/CAM restorations have a high clinical success rate after 12 months. A longer clinical evaluation period is necessary to draw further conclusions.

Core-shell structured MnSiO3 supported with CNTs as a high capacity anode for lithium-ion batteries.

PubMed

Feng, Jing; Li, Qin; Wang, Huijun; Zhang, Min; Yang, Xia; Yuan, Ruo; Chai, Yaqin

2018-04-17

Metal silicates are good candidates for use in lithium ion batteries (LIBs), however, their electrochemical performance is hindered by their poor electrical conductivity and volume expansion during Li+ insertion/desertion. In this work, one-dimensional core-shell structured MnSiO3 supported with carbon nanotubes (CNTs) (referred to as CNT@MnSiO3) with good conductivity and electrochemical performance has been successfully synthesized using a solvothermal process under moderate conditions. In contrast to traditional composites of CNTs and nanoparticles, the CNT@MnSiO3 composite in this work is made up of CNTs with a layer of MnSiO3 on the surface. The one-dimensional CNT@MnSiO3 nanotubes provide a useful channel for transferring Li+ ions during the discharge/charge process, which accelerates the Li+ diffusion speed. The CNTs inside the structure not only enhance the conductivity of the composite, but also prevent volume expansion. A high reversible capacity (920 mA h g-1 at 500 mA g-1 over 650 cycles) and good rate performance were obtained for CNT@MnSiO3, showing that this strategy of synthesizing coaxial CNT@MnSiO3 nanotubes offers a promising method for preparing other silicates for LIBs or other applications.

Optical band gap studies on lithium aluminum silicate glasses doped with Cr3+ ions

NASA Astrophysics Data System (ADS)

El-Diasty, Fouad; Abdel Wahab, Fathy A.; Abdel-Baki, Manal

2006-11-01

Lithium aluminum silicate glass system (LAS) implanted with chromium ions is prepared. The reflectance and transmittance measurements are used to determine the dispersion of absorption coefficient. The optical data are explained in terms of the different oxidation states adopted by the chromium ions into the glass network. It is found that the oxidation state of the chromium depends on its concentration. Across a wide spectral range, 0.2-1.6μm, analysis of the fundamental absorption edge provides values for the average energy band gaps for allowed direct and indirect transitions. The optical absorption coefficient just below the absorption edge varies exponentially with photon energy indicating the presence of Urbach's tail. Such tail is decreased with the increase of the chromium dopant. From the analysis of the optical absorption data, the absorption peak at ground state exciton energy, the absorption at band gap, and the free exciton binding energy are determined. The extinction coefficient data are used to determine the Fermi energy level of the studied glasses. The metallization criterion is obtained and discussed exploring the nature of the glasses. The measured IR spectra of the different glasses are used to throw some light on the optical properties of the present glasses correlating them with their structure and composition.

Optical band gap and spectroscopic study of lithium alumino silicate glass containing Y 3+ ions

NASA Astrophysics Data System (ADS)

Shakeri, M. S.; Rezvani, M.

2011-09-01

The effect of different amounts of Y 2O 3 dopant on lithium alumino silicate (LAS) glass has been studied in this work. Glasses having 14.8Li 2O-20Al 2O 3-65.2SiO 2 (wt%) composition accompanied with Y 2O 3 dopant were prepared by normal melting process. In order to calculate the absorption coefficient of samples, transmittance and reflectance spectra of polished samples were measured in the room temperature. Optical properties i.e. Fermi energy level, direct and indirect optical band gaps and Urbach energy were calculated using functionality of extinction coefficient from Fermi-Dirac distribution function, Tauc's plot and the exponential part of absorption coefficient diagram, respectively. It has been clarified that variation in mentioned optical parameters is associated with the changes in physical properties of samples i.e. density or molar mass. On the other hand, increasing of Y 3+ ions in the glassy microstructure of samples provides a semiconducting character to LAS glass by reducing the direct and indirect optical band gaps of glass samples from 1.97 to 1.67 and 3.46 to 2.1 (eV), respectively. These changes could be attributed to the role of Y 3+ ions as the network former in the track of SiO 4 tetrahedrals.

Three-dimensionally ordered macroporous Li2FeSiO4/C composite as a high performance cathode for advanced lithium ion batteries

NASA Astrophysics Data System (ADS)

Ding, Zhengping; Liu, Jiatu; Ji, Ran; Zeng, Xiaohui; Yang, Shuanglei; Pan, Anqiang; Ivey, Douglas G.; Wei, Weifeng

2016-10-01

Li2MSiO4 (M = Mn, Fe, Co, Ni, et al.) has received great attention because of the theoretical possibility to reversibly deintercalate two Li+ ions from the structure. However, the silicates still suffer from low electronic conductivity, sluggish lithium ion diffusion and structural instability upon deep cycling. In order to solve these problems, a "hard-soft" templating method has been developed to synthesize three-dimensionally ordered macroporous (3DOM) Li2FeSiO4/C composites. The 3DOM Li2FeSiO4/C composites show a high reversible capacity (239 mAh g-1) with ∼1.50 lithium ion insertion/extraction, a capacity retention of nearly 100% after 420 cycles and excellent rate capability. The enhanced electrochemical performance is ascribed to the interconnected carbon framework that improves the electronic conductivity and the 3DOM structure that offers short Li ion diffusion pathways and restrains volumetric changes.

SEAL Studies of Variant Blanket Concepts and Materials

NASA Astrophysics Data System (ADS)

Cook, I.; Taylor, N. P.; Forty, C. B. A.; Han, W. E.

1997-09-01

Within the European SEAL ( Safety and Environmental Assessment of fusion power, Long-term) program, safety and environmental assessments have been performed which extend the results of the earlier SEAFP (Safety and Environmental Assessment of Fusion Power) program to a wider range of blanket designs and material choices. The four blanket designs analysed were those which had been developed within the Blanket program of the European Fusion Programme. All four are based on martensitic steel as structural material, and otherwise may be summarized as: water-cooled lithium-lead; dual-cooled lithium-lead; helium-cooled lithium silicate (BOT geometry); helium-cooled lithium aluminate (or zirconate) (BIT geometry). The results reveal that all the blankets show the favorable S&E characteristics of fusion, though there are interesting and significant differences between them. The key results are described. Assessments have also been performed of a wider range of materials than was considered in SEAFP. These were: an alternative vanadium alloy, an alternative low-activation martensitic steel, titanium-aluminum intermetallic, and SiC composite. Assessed impurities were included in the compositions, and these had very important effects upon some of the results. Key results impacting upon accident characteristics, recycling, and waste management are described.

Predicting the Sources and Formation Mechanisms of Evolved Lunar Crust by Linking K/Ca Ratios of Lunar Granites to Analogous Terrestrial Igneous Rocks

NASA Technical Reports Server (NTRS)

Mills, R. D.; Simon, J. I.

2012-01-01

Although silicic rocks (i.e. granites and rhyolites) comprise a minor component of the sampled portion of the lunar crust, recent remote sensing studies [e.g., 1-4] indicate that several un-sampled regions of the Moon have significantly higher concentrations of silicic material (also high in [K], [U], and [Th]) than sampled regions. Within these areas are morphological features that are best explained by the existence of chemically evolved volcanic rocks. Observations of silicic domes [e.g., 1-5] suggest that sizable networks of silicic melt were present during crust formation. Isotopic data indicate that silicic melts were generated over a prolonged timespan from 4.3 to 3.9 Ga [e.g., 6-8]. The protracted age range and broad distribution of silicic rocks on the Moon indicate that their petrogenesis was an important mechanism for secondary crust formation. Understanding the origin and evolution of such silicic magmas is critical to determining the composition of the lunar crustal highlands and will help to distinguish between opposing ideas for the Moon's bulk composition and differentiation. The two main hypotheses for generating silicic melts on Earth are fractional crystallization or partial melting. On the Moon silicic melts are thought to have been generated during extreme fractional crystallization involving end-stage silicate liquid immiscibility (SLI) [e.g. 9, 10]. However, SLI cannot account for the production of significant volumes of silicic melt and its wide distribution, as reported by the remote global surveys [1, 2, 3]. In addition, experimental and natural products of SLI show that U and Th, which are abundant in the lunar granites and seen in the remote sensing data of the domes, are preferentially partitioned into the depolymerized ferrobasaltic magma and not the silicic portion [11, 12]. If SLI is not the mechanism that generated silicic magmas on the Moon then alternative processes such as fractional crystallization (only crystal-liquid separation) or partial melting should be considered as viable possibilities to be tested.

Comparison of light harmonic generation in Al and Ge consisted silicate materials

NASA Astrophysics Data System (ADS)

Smirnov, Vitaly A.; Vostrikova, Liubov I.

2018-04-01

The silicate materials are perspective for different areas of laser physics and photonics. In this paper the comparison of the nonlinear conversion with the generation of the light harmonic in Al- and Ge-containing silicate materials is presented. The peculiarities of the processes of the light harmonic generation in dependence on the concentrations of the chemical components are discussed and the influences of the additional small inclusion of the elements of fifth group and the rare-earth elements are estimated.

Natural graphene microsheets/sulfur as Li-S battery cathode towards >99% coulombic efficiency of long cycles

NASA Astrophysics Data System (ADS)

Zhang, Yan; Duan, Xiaoyong; Wang, Jie; Wang, Congwei; Wang, Junying; Wang, Jianlong; Wang, Junzhong

2018-02-01

Lithium-sulfur battery receives intense attention owing to its high theoretical energy density. However, poor electrical conductivity of sulfur and poor cycle stability of the battery hinder its application. Here, we report that graphene microsheets prepared from microcrystalline graphite minerals by an electrochemical & mechanical approach work as a special conductive support to load sulfur as the cathode of lithium-sulfur battery. The graphene microsheets have the features of excellent conductivity and low defect, small sheet sizes of <1 μm2 and ≤6 atomic layers as well as natural silicate residue covered. Li-S batteries of graphene microsheets/S as cathode exhibit long-term cyclability and high coulombic efficiency. At 1 C for 2000 cycles, average coulombic efficiency of 99.7% is reached.

EPR of radiation defects in lithium-oxyfluoride glass ceramics

NASA Astrophysics Data System (ADS)

Fedotovs, A.; Rogulis, U.; Sarakovskis, A.; Dimitrocenko, L.

2010-11-01

We studied oxyfluoride composites based on lithium silicate glasses with yttrium fluorides and rare-earth dopants. The electron paramagnetic resonance (EPR) has been used to obtain information about radiation induced defects in these materials. Spectra have been measured before and after X-ray irradiation at room temperature and at liquid nitrogen temperature. Fluoride crystallites within samples were created by means of thermal treatment at specific temperatures. EPR spectra of radiation induced defects in oxyfluoride glass ceramics, in which crystallites have not been yet created, show no explicit hfs interaction of fluorine nuclei. However, in glass ceramics, which already contains fluoride crystallites, the hfs characteristic to fluorine nuclei appears in the EPR spectra. EPR hyperfine structure could be explained within a model of an F-type centre in YF3 crystalline phase.

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus.

PubMed

Shellnutt, J Gregory

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra.

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus

PubMed Central

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra. PMID:29584745

Real time neutron diffraction and NMR of the Empress II glass-ceramic system.

PubMed

O'Donnell, M D; Hill, R G; Karpukhina, N; Law, R V

2011-10-01

This study reports real time neutron diffraction on the Empress II glass-ceramic system. The commercial glass-ceramics was characterized by real time neutron diffraction, ³¹P and ²⁹Si solid-state MAS-NMR, DSC and XRD. On heating, the as-received glass ceramic contained lithium disilicate (Li₂Si₂O₅), which melted with increasing temperature. This was revealed by neutron diffraction which showed the Bragg peaks for this phase had disappeared by 958°C in agreement with thermal analysis. On cooling lithium metasilicate (Li₂SiO₃) started to form at around 916°C and a minor phase of cristobalite at around 852°C. The unit cell volume of both Li-silicate phases increased linearly with temperature at a rate of +17×10⁻³ ų.°C⁻¹. Room temperature powder X-ray diffraction (XRD) of the material after cooling confirms presence of the lithium metasilicate and cristobalite as the main phases and shows, in addition, small amount of lithium disilicate and orthophosphate. ³¹P MAS-NMR reveals presence of the lithiorthophosphate (Li₃PO₄) before and after heat treatment. The melting of lithium disilicate on heating and crystallisation of lithium metasilicate on cooling agree with endothermic and exotermic features respectively observed by DSC. ²⁹Si MAS-NMR shows presence of lithium disilicate phase in the as-received glass-ceramic, though not in the major proportion, and lithium metasilicate in the material after heat treatment. Both phases have significantly long T₁ relaxation time, especially the lithium metasilicate, therefore, a quantitative analysis of the ²⁹Si MAS-NMR spectra was not attempted. Significance. The findings of the present work demonstrate importance of the commercially designed processing parameters in order to preserve desired characteristics of the material. Processing the Empress II at a rate slower than recommended 60°C min⁻¹ or long isothermal hold at the maximal processing temperature 920°C can cause crystallization of lithium metasilicate and cristobalite instead of lithium disilicate as major phase. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Thermophysical Properties of Matter - the TPRC Data Series. Volume 13. Thermal Expansion - Nonmetallic Solids

DTIC Science & Technology

1977-01-01

topography of the state of knowledge on the thermal expansion of nonmetallic solids. We believe there is also much food for reflec- West Lafayette...34 Lithium Silicates ......... 713 209 Magnesium Metasilicate MgSiO. .. ......... 715 210 Magnesium Orthosilicate Mg2 SiO . . . . . . . . . . . . 718 211...Antiferromagnetism of Praseodymium," Phys. Rev. Letters, 12(20), 553-5, 1964. 66. Goode, J.M., "Phase Transition Temperature of Polonium ,"J. Chem. Phys., 26(5), 1269

Optical band gap and spectroscopic study of lithium alumino silicate glass containing Y3+ ions.

PubMed

Shakeri, M S; Rezvani, M

2011-09-01

The effect of different amounts of Y2O3 dopant on lithium alumino silicate (LAS) glass has been studied in this work. Glasses having 14.8Li2O-20Al2O3-65.2SiO2 (wt%) composition accompanied with Y2O3 dopant were prepared by normal melting process. In order to calculate the absorption coefficient of samples, transmittance and reflectance spectra of polished samples were measured in the room temperature. Optical properties i.e. Fermi energy level, direct and indirect optical band gaps and Urbach energy were calculated using functionality of extinction coefficient from Fermi-Dirac distribution function, Tauc's plot and the exponential part of absorption coefficient diagram, respectively. It has been clarified that variation in mentioned optical parameters is associated with the changes in physical properties of samples i.e. density or molar mass. On the other hand, increasing of Y3+ ions in the glassy microstructure of samples provides a semiconducting character to LAS glass by reducing the direct and indirect optical band gaps of glass samples from 1.97 to 1.67 and 3.46 to 2.1 (eV), respectively. These changes could be attributed to the role of Y3+ ions as the network former in the track of SiO4 tetrahedrals. Copyright © 2011 Elsevier B.V. All rights reserved.

Enamel and Dentin Surface Finishing Influence on the Roughness and Microshear Bond Strength of a Lithium Silicate Glass-Ceramic for Laminate Veneers

PubMed Central

Gonzaga, Carla Castiglia; Bravo, Ruth Peggy; Pavelski, Thiago Vinícius; Garcia, Paula Pontes; Correr, Gisele Maria; Leonardi, Denise Piotto; da Cunha, Leonardo Fernandes; Furuse, Adilson Yoshio

2015-01-01

Objectives. This study evaluated the influence of cavity surface finishing with diamond burs of different grit mounted on high-speed turbine and ultrasound on the roughness and microshear bond strength (MBS) of a lithium silicate glass-ceramic to enamel and dentin. Methods. Enamel and dentin specimens were divided into seven groups, according to the type of surface finishing: 1200-grit sandpaper (control), two different brands of medium-grit and fine-grit diamond burs in a high-speed turbine; medium-grit and fine-grit CVD (chemical vapor deposition) tips in an ultrasonic device. Roughness parameters (n = 5) and MSBS to a glass-ceramic (n = 10) were determined. Data were analyzed using ANOVA and Tukey's test (α = 5%). Results. Control group showed lower mean roughness readings and groups that used medium-grit diamond burs showed the highest mean roughness values. Regarding MSBS, there was no statistical difference when comparing the groups gritted with the same brand of medium- and fine-grit burs and tips. Conclusions. Cavity surface finishing influenced the roughness parameters and MSBS of a glass-ceramic to enamel and dentin. Medium-grit diamond burs in high-speed turbine showed the highest mean roughness values. Fine-grit CVD tips in ultrasound presented the highest MSBS values for both enamel and dentin. PMID:27347507

Enamel and Dentin Surface Finishing Influence on the Roughness and Microshear Bond Strength of a Lithium Silicate Glass-Ceramic for Laminate Veneers.

PubMed

Gonzaga, Carla Castiglia; Bravo, Ruth Peggy; Pavelski, Thiago Vinícius; Garcia, Paula Pontes; Correr, Gisele Maria; Leonardi, Denise Piotto; da Cunha, Leonardo Fernandes; Furuse, Adilson Yoshio

2015-01-01

Objectives. This study evaluated the influence of cavity surface finishing with diamond burs of different grit mounted on high-speed turbine and ultrasound on the roughness and microshear bond strength (MBS) of a lithium silicate glass-ceramic to enamel and dentin. Methods. Enamel and dentin specimens were divided into seven groups, according to the type of surface finishing: 1200-grit sandpaper (control), two different brands of medium-grit and fine-grit diamond burs in a high-speed turbine; medium-grit and fine-grit CVD (chemical vapor deposition) tips in an ultrasonic device. Roughness parameters (n = 5) and MSBS to a glass-ceramic (n = 10) were determined. Data were analyzed using ANOVA and Tukey's test (α = 5%). Results. Control group showed lower mean roughness readings and groups that used medium-grit diamond burs showed the highest mean roughness values. Regarding MSBS, there was no statistical difference when comparing the groups gritted with the same brand of medium- and fine-grit burs and tips. Conclusions. Cavity surface finishing influenced the roughness parameters and MSBS of a glass-ceramic to enamel and dentin. Medium-grit diamond burs in high-speed turbine showed the highest mean roughness values. Fine-grit CVD tips in ultrasound presented the highest MSBS values for both enamel and dentin.

Efficient generation of far-infrared radiation in the vicinity of polariton resonance of lithium niobate.

PubMed

Lin, Xiaomu; Wang, Lei; Ding, Yujie J

2012-09-01

We efficiently generated far-infrared radiation at the wavelengths centered at 20.8 μm in the vicinity of one of the polariton resonances of lithium niobate. Such an efficient nonlinear conversion is made possible by exploiting phase matching for difference-frequency generation in lithium niobate. The highest peak power reached 233 W.

Lithium Iron Orthosilicate Cathode: Progress and Perspectives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ni, Jiangfeng; Jiang, Yu; Bi, Xuanxuan

2017-07-18

The pursuit of cathodes with a high capacity is remarkably driven by the ever increasing demand of high-energy lithium ion batteries in electronics and transportation. In this regard, polyanionic lithium iron orthosilicate (Li2FeSiO4) offers a promising opportunity because it affords a high theoretical capacity of 331 mAh g–1. However, such a high theoretical capacity of Li2FeSiO4 has frequently been compromised in practice because of the extremely low electronic and ionic conductivity. To address this issue, material engineering strategies to boost the Li storage kinetics in Li2FeSiO4 have proven indispensable. In this Perspective, we will briefly present the structural characteristics, intrinsicmore » physicochemical properties, and electrochemical behavior of Li2FeSiO4. We particularly focus on recent materials engineering of silicates, which is implemented mainly through advanced synthetic techniques and elaborate controls. This Perspective highlights the importance of integrating theoretical analysis into experimental implementation to further advance the Li2FeSiO4 materials.« less

Lithium isotope fractionation by diffusion in minerals Part 2: Olivine

NASA Astrophysics Data System (ADS)

Richter, Frank; Chaussidon, Marc; Bruce Watson, E.; Mendybaev, Ruslan; Homolova, Veronika

2017-12-01

Recent experiments have shown that lithium isotopes can be significantly fractionated by diffusion in silicate liquids and in augite. Here we report new laboratory experiments that document similarly large lithium isotopic fractionation by diffusion in olivine. Two types of experiments were used. A powder-source method where lithium from finely ground spodumene (LiAlSi2O6) diffused into oriented San Carlos olivine, and piston cylinder annealing experiments where Kunlun clinopyroxene (∼30 ppm lithium) and oriented San Carlos olivine (∼2 ppm lithium) were juxtaposed. The lithium concentration along traverses across the run products was measured using both laser ablation as a source for a Varian 820-MS quadrupole mass spectrometer and a CAMECA 1270 secondary ion mass spectrometer. The CAMECA 1270 was also used to measure the lithium isotopic fractionation across olivine grains recovered from the experiments. The lithium isotopes were found to be fractionationed by many tens of permil in the diffusion boundary layer at the grain edges as a result of 6Li diffusing significantly faster than 7Li. The lithium concentration and isotopic fractionation data across the olivine recovered from the different experiments were modeled using calculations in which lithium was assumed to be of two distinct types - one being fast diffusing interstitial lithium, the other much less mobile lithium on a metal site. The two-site diffusion model involves a large number of independent parameters and we found that different choices of the parameters can produce very comparable fits to the lithium concentration profiles and associated isotopic fractionation. Because of this nonuniqueness we are able to determine only a range for the relative diffusivity of 6Li compared to 7Li. When the mass dependence of lithium diffusion is parameterized as D6Li /D7Li =(7 / 6) β , the isotope fractionation for diffusion along the a and c crystallographic direction of olivine can be fit by β = 0.4 ± 0.1 while the fractionation in the b direction appears to be somewhat lower. Model calculations were also used to fit the lithium concentration and isotopic fractionation across a natural olivine grain from a peridotite xenolith from the Eastern North China Craton. The isotopic data were fit using β values (0.3-0.36) similar to that of the laboratory experiments. This, along with the fact that the isotopic fractionation is restricted to that part of the mineral with a gradient in lithium concentration, is strong evidence that the lithium zoning of this mineral grain is the result of lithium loss by diffusion and thus that it can be used, as illustrated, to constrain the cooling history.

A sulfur host based on titanium monoxide@carbon hollow spheres for advanced lithium-sulfur batteries.

PubMed

Li, Zhen; Zhang, Jintao; Guan, Buyuan; Wang, Da; Liu, Li-Min; Lou, Xiong Wen David

2016-10-20

Lithium-sulfur batteries show advantages for next-generation electrical energy storage due to their high energy density and cost effectiveness. Enhancing the conductivity of the sulfur cathode and moderating the dissolution of lithium polysulfides are two key factors for the success of lithium-sulfur batteries. Here we report a sulfur host that overcomes both obstacles at once. With inherent metallic conductivity and strong adsorption capability for lithium-polysulfides, titanium monoxide@carbon hollow nanospheres can not only generate sufficient electrical contact to the insulating sulfur for high capacity, but also effectively confine lithium-polysulfides for prolonged cycle life. Additionally, the designed composite cathode further maximizes the lithium-polysulfide restriction capability by using the polar shells to prevent their outward diffusion, which avoids the need for chemically bonding all lithium-polysulfides on the surfaces of polar particles.

A sulfur host based on titanium monoxide@carbon hollow spheres for advanced lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Li, Zhen; Zhang, Jintao; Guan, Buyuan; Wang, Da; Liu, Li-Min; Lou, Xiong Wen (David)

2016-10-01

Lithium-sulfur batteries show advantages for next-generation electrical energy storage due to their high energy density and cost effectiveness. Enhancing the conductivity of the sulfur cathode and moderating the dissolution of lithium polysulfides are two key factors for the success of lithium-sulfur batteries. Here we report a sulfur host that overcomes both obstacles at once. With inherent metallic conductivity and strong adsorption capability for lithium-polysulfides, titanium monoxide@carbon hollow nanospheres can not only generate sufficient electrical contact to the insulating sulfur for high capacity, but also effectively confine lithium-polysulfides for prolonged cycle life. Additionally, the designed composite cathode further maximizes the lithium-polysulfide restriction capability by using the polar shells to prevent their outward diffusion, which avoids the need for chemically bonding all lithium-polysulfides on the surfaces of polar particles.

Discovery of high-gain stimulated polariton scattering near 4  THz from lithium niobate.

PubMed

Chiu, Yu-Chung; Wang, Tsong-Dong; Zhao, Gang; Huang, Yen-Chieh

2017-12-01

Lithium niobate is the most popular material for terahertz wave generation via stimulated polariton scattering (SPS), previously known to have a gain peak near 2 THz. Here we report the discovery of another phase-matched gain peak near 4 THz in lithium niobate, which greatly extends the useful gain spectrum of lithium niobate. Despite the relatively high 4 THz absorption in lithium niobate, the 4 THz SPS becomes dominant over the 2 THz one in an intensely pumped short lithium niobate crystal due to less diffraction-induced absorption and mode-area mismatch. We also demonstrate a signal-seeded OTPO that generates 1.4 nJ at 4.2 THz from lithium niobate with 17.5 mJ pump energy.

Ag-doped Lithium alumino silicate photostructurable glass for microdevice fabrication

NASA Astrophysics Data System (ADS)

Mishra, Richa; Goswami, Madhumita; Krishnan, Madangopal

2018-04-01

Ag-doped LAS glass of composition (wt.%):74SiO2-6Al2O3-15Li2O-5X (X=other additives) were prepared by melt-quench technique and characterized for thermal and optical properties using DTA and UV-Visible spectrometer. XRD technique was used for phase identification in the heat treated glasses. Glass samples were exposed to UV-light for conversion of Ce3+ to Ce4+ state and Ag+ into Ago metallic state. DTA shows a lower crystallization temperature (Tp) at around 605°C for exposed samples as compared to unexposed base glass which is at around 625°C. UV-Visible spectra shows a broad band at around 305nm which indicates Ce3+ in base glass whereas in case of UV-exposed sample the reduced peak intensity indicates conversion of Ce3+ to Ce4+ ions, which also confirm formation of Ago in glass samples. Ag agglomeration was also confirmed from the band position at 430nm in heat treated sample, found responsible for early growth of meta-silicate phase in exposed sample. The meta-silicate phase was selectively etched for fabrication of micro-devices.

Carbon substitution for oxygen in silicates in planetary interiors

PubMed Central

Sen, Sabyasachi; Widgeon, Scarlett J.; Navrotsky, Alexandra; Mera, Gabriela; Tavakoli, Amir; Ionescu, Emanuel; Riedel, Ralf

2013-01-01

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiOxC4-x tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiOxC4-x tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10–100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle. PMID:24043830

Carbon substitution for oxygen in silicates in planetary interiors.

PubMed

Sen, Sabyasachi; Widgeon, Scarlett J; Navrotsky, Alexandra; Mera, Gabriela; Tavakoli, Amir; Ionescu, Emanuel; Riedel, Ralf

2013-10-01

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiO(x)C(4-x) tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiO(x)C(4-x) tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10-100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle.

Thermal Aspects of Lithium Ion Cells

NASA Technical Reports Server (NTRS)

Frank, H.; Shakkottai, P.; Bugga, R.; Smart, M.; Huang, C. K.; Timmerman, P.; Surampudi, S.

2000-01-01

This viewgraph presentation outlines the development of a thermal model of Li-ion cells in terms of heat generation, thermal mass, and thermal resistance. Intended for incorporation into battery model. The approach was to estimate heat generation: with semi-theoretical model, and then to check accuracy with efficiency measurements. Another objective was to compute thermal mass from component weights and specific heats, and to compute the thermal resistance from component dimensions and conductivities. Two lithium batteries are compared, the Cylindrical lithium battery, and the prismatic lithium cell. It reviews methodology for estimating the heat generation rate. Graphs of the Open-circuit curves of the cells and the heat evolution during discharge are given.

Misfit and fracture load of implant-supported monolithic crowns in zirconia-reinforced lithium silicate

PubMed Central

GOMES, Rafael Soares; de SOUZA, Caroline Mathias Carvalho; BERGAMO, Edmara Tatiely Pedroso; BORDIN, Dimorvan; DEL BEL CURY, Altair Antoninha

2017-01-01

Abstract Zirconia-reinforced lithium silicate (ZLS) is a ceramic that promises to have better mechanical properties than other materials with the same indications as well as improved adaptation and fracture strength. Objective In this study, marginal and internal misfit and fracture load with and without thermal-mechanical aging (TMA) of monolithic ZLS and lithium disilicate (LDS) crowns were evaluated. Material and methods Crowns were milled using a computer-aided design/computer-aided manufacturing system. Marginal gaps (MGs), absolute marginal discrepancy (AMD), axial gaps, and occlusal gaps were measured by X-ray microtomography (n=8). For fracture load testing, crowns were cemented in a universal abutment, and divided into four groups: ZLS without TMA, ZLS with TMA, LDS without TMA, and LDS with TMA (n=10). TMA groups were subjected to 10,000 thermal cycles (5-55°C) and 1,000,000 mechanical cycles (200 N, 3.8 Hz). All groups were subjected to compressive strength testing in a universal testing machine at a crosshead speed of 1 mm/min until failure. Student’s t-test was used to examine misfit, two-way analysis of variance was used to analyze fracture load, and Pearson’s correlation coefficients for misfit and fracture load were calculated (α=0.05). The materials were analyzed according to Weibull distribution, with 95% confidence intervals. Results Average MG (p<0.001) and AMD (p=0.003) values were greater in ZLS than in LDS crowns. TMA did not affect the fracture load of either material. However, fracture loads of ZLS crowns were lower than those of LDS crowns (p<0.001). Fracture load was moderately correlated with MG (r=-0.553) and AMD (r=-0.497). ZLS with TMA was least reliable, according to Weibull probability. Conclusion Within the limitations of this study, ZLS crowns had lower fracture load values and greater marginal misfit than did LDS crowns, although these values were within acceptable limits. PMID:28678947

Lithium or Valproate Adjunctive Therapy to Second-generation Antipsychotics and Metabolic Variables in Patients With Schizophrenia or Schizoaffective Disorder

PubMed Central

VINCENZI, BRENDA; GREENE, CLAIRE M.; ULLOA, MELISSA; PARNAROUSKIS, LINDSEY; JACKSON, JOHN W.; HENDERSON, DAVID C.

2017-01-01

Objective People with schizophrenia are at greater risk for cardiovascular disease and their overallmortality rate is elevated compared to the general population. The metabolic side effects of antipsychotic medications have been widely studied; however, the effect of adding conventional mood stabilizers, such as lithium and valproate, to antipsychotic medication has not been assessed in terms of metabolic risk. The primary purpose of this secondary analysis was to examine whether treatment with lithium or valproate in addition to a second-generation antipsychotic is associated with poorer metabolic outcomes than treatment with a second-generation antipsychotic without lithium or depakote. Methods Baseline data from 3 studies, which included measurement of body mass index, waist circumference, fasting glucose, insulin, homeostatic model assessment of insulin resistance, insulin sensitivity index, glucose utilization, and acute insulin response to glucose, were included in the analysis. Results No differences were found between those taking lithium or valproate and those who were not in terms of fasting glucose, fasting insulin, and homeostatic model assessment of insulin resistance. Insulin sensitivity was lower among participants taking lithium or valproate. Participants taking lithium or valproate had a higher body mass index than those not taking conventional mood stabilizers, although the difference did not reach statistical significance. Conclusions These cross-sectional findings suggest it may be beneficial to monitor insulin sensitivity and body mass index in patients taking lithium or valproate in combination with a second-generation antipsychotic. PMID:27123797

X-Ray Absorption Spectroscopy Studies of the Atomic Structure of Zirconium-Doped Lithium Silicate Glasses and Glass-Ceramics, Zirconium-Doped Lithium Borate Glasses, and Vitreous Rare-Earth Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon

In the first part of this work, the atomic-scale structure around rare-earth (RE = Pr, Nd, Eu, Dy, and Er) cations (RE3+) in rare-earth sodium ultraphosphate (REUP) glasses were investigated using RE LIII -edge (RE = Nd, Er, Dy, and Eu) and K-edge (RE = Pr and Dy) Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. (RE2O 3)x(Na2O)y(P2O5) 1-x-y glasses in the compositional range 0 ≤ x ≤ 0.14 and 0.3 ≤ x + y ≤ 0.4 were studied. For the nearest oxygen shell, the RE-oxygen (RE-O) coordination number decreases from 10.8 to 6.5 with increasing RE content for Pr-, Nd-, Dy-, and Er-doped sodium ultraphosphate glasses. For Eu-doped samples, the Eu-O coordination number was between 7.5 and 8.8. Also, the RE-O mean distance ranges were between 2.43-2.45 A, 2.40-2.43 A, 2.36-2.38 A, 2.30-2.35 A, and 2.28-2.30 A for Pr-, Nd-, Eu-, Dy-, and Er-doped samples, respectively. In the second part, a series of Zr-doped (3-10 mol%) lithium silicate (ZRLS) glass-ceramics and their parent glasses and a series of Zr-doped (2-6 mol% ZrO2) lithium borate (ZRLB) glasses were investigated using Zr K-edge EXAFS and X-ray Absorption Near Edge Structure (XANES) spectroscopy. Immediate coordination environments of all ZRLS glasses are remarkably similar for different compositions. For the nearest oxygen shell, the Zr-O coordination number ranges were between 6.1 and 6.3 for nucleated and crystallized samples, respectively. Also, the Zr-O mean distance remains similar around 2.10 A. For these glasses, the composition dependence of structural parameters was small. Small changes in the coordination environment were observed for ZRLS glass-ceramics after thermal treatments. In contrast, Zr coordination environment in ZRLB glasses appear to depend appreciably on the Zr concentration. For the nearest oxygen shell, the Zr-O coordination number increased from 6.1 to 6.8 and the Zr-O distance decreased from 2.18 A to 2.14 A with decreasing ZrO2 content.

The effects of saxitoxin and tetrodotoxin on nerve conduction in the presence of lithium ions and of magnesium ions

PubMed Central

Evans, M. H.

1969-01-01

1. It has been shown that nerve fibres from rat cauda equina will conduct action potentials after immersion in saline in which lithium chloride is substituted for sodium chloride. 2. Both saxitoxin and tetrodotoxin inhibit lithium-generated action potentials. The concentration of toxin needed to inhibit the lithium-generated action potentials is similar to that needed to inhibit sodium-generated action potentials. 3. If magnesium chloride is added to the saline to give a concentration of 10-15 mM there is usually a slight fall in amplitude of the compound action potential. Saxitoxin and tetrodotoxin now inhibit the action potential to a greater degree than in the absence of magnesium ions. PMID:5789802

Integrating a redox-coupled dye-sensitized photoelectrode into a lithium-oxygen battery for photoassisted charging.

PubMed

Yu, Mingzhe; Ren, Xiaodi; Ma, Lu; Wu, Yiying

2014-10-03

With a high theoretical specific energy, the non-aqueous rechargeable lithium-oxygen battery is a promising next-generation energy storage technique. However, the large charging overpotential remains a challenge due to the difficulty in electrochemically oxidizing the insulating lithium peroxide. Recently, a redox shuttle has been introduced into the electrolyte to chemically oxidize lithium peroxide. Here, we report the use of a triiodide/iodide redox shuttle to couple a built-in dye-sensitized titanium dioxide photoelectrode with the oxygen electrode for the photoassisted charging of a lithium-oxygen battery. On charging under illumination, triiodide ions are generated on the photoelectrode, and subsequently oxidize lithium peroxide. Due to the contribution of the photovoltage, the charging overpotential is greatly reduced. The use of a redox shuttle to couple a photoelectrode and an oxygen electrode offers a unique strategy to address the overpotential issue of non-aqueous lithium-oxygen batteries and also a distinct approach for integrating solar cells and batteries.

Assessment of the 3H and 7Be generation in the IFMIF lithium loop

NASA Astrophysics Data System (ADS)

Simakov, S. P.; Fischer, U.; von Möllendorff, U.

2004-08-01

A complete evaluation of the 7Be and tritium inventory induced in the IFMIF lithium loop by deuterons and neutrons was performed on the basis of 3D Monte Carlo calculations with the M CDeLicious code and evaluated d-Li and n-Li cross-section data. The associated reaction cross-sections and thick lithium target yields were checked against available experimental data. The IFMIF calculations showed that the deuteron beam will produce 1.5 g of 7Be and 6 g of 3H per full power year in the lithium jet. The tritium generation in the whole lithium loop due to neutron induced reactions is at a rate of 1.5 g/fpy. The radio-active decay results in an equilibrium concentration 0.3 mg of 7Be and 50 mg of 3H per 1 kg of circulating lithium if no radioactive products are removed from the loop.

High Temperature Thermosetting Polyimide Nanocomposites Prepared with Reduced Charge Organoclay

NASA Technical Reports Server (NTRS)

Campbell, Sandi; Liang, Margaret I.

2005-01-01

The naturally occurring sodium and calcium cations found in bentonite clay galleries were exchanged with lithium cations. Following the cation exchange, a series of reduced charge clays were prepared by heat treatment of the lithium bentonite at 130 C, 150 C, or 170 C. Inductively coupled plasma (ICP) analysis showed that heating the lithium clay at elevated temperatures reduced its cation exchange capacity. Ion exchange of heat-treated clays with either a protonated alkyl amine or a protonated aromatic diamine resulted in decreasing amounts of the organic modifier incorporated into the lithium clay. The level of silicate dispersion in a thermosetting polyimide matrix was dependent upon the temperature of Li-clay heat treatment as well as the organic modification. In general, clays treated at 150 C or 170 C, and exchanged with protonated octadcylamine or protonated 2,2'-dimethlybenzidine (DMBZ) showed a higher degree of dispersion than clays treated at 130 C, or exchanged with protonated dodecylamine. Dynamic mechanical analysis showed little change in the storage modulus or T(sub g) of the nanocomposites compared to the base resin. However, long term isothermal aging of the samples showed a significant decrease in the resin oxidative weight loss. Nanocomposite samples aged in air for 1000 hours at 288 C showed of to a decrease in weight loss compared to that of the base resin. This again was dependent on the temperature at which the Li-clay was heated and the choice of organic modification.

Solution based synthesis of mixed-phase materials in the Li2TiO3-Li4SiO4 system

NASA Astrophysics Data System (ADS)

Hanaor, Dorian A. H.; Kolb, Matthias H. H.; Gan, Yixiang; Kamlah, Marc; Knitter, Regina

2015-01-01

As candidate tritium breeder materials for use in the ITER helium cooled pebble bed, ceramic multiphasic compounds lying in the region of the quasi-binary lithium metatitanate-lithium orthosilicate system may exhibit mechanical and physical advantages relative to single phase materials. Here we present an organometallic solution-based synthesis procedure for the low-temperature fabrication of compounds in the Li2TiO3-Li4SiO4 region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li2TiO3 and Li2SiO3 readily crystallise in nanocrystalline form at temperatures below 180 °C. Lithium deficiency in the region of 5% results from Li sublimation from Li4SiO4 and/or from excess Li incorporation in the metatitanate phase and brings about a stoichiometry shift, with product compounds exhibiting mixed lithium orthosilicate/metasilicate content towards the Si rich region and predominantly Li2TiO3 content towards the Ti rich region. Above 1150 °C the transformation of monoclinic to cubic γ-Li2TiO3 disordered solid-solution occurs while the melting of silicate phases indicates a likely monotectic type system with a solidus line in the region 1050-1100 °C. Synthesis procedures involving a lithium chloride precursor are not likely to be a viable option for breeder pebble synthesis as this route was found to yield materials with a more significant Li-deficiency exhibiting the crystallisation of the Li2TiSiO5 phase at intermediate compositions.

Compositions of micas in peraluminous granitoids of the eastern Arabian shield - Implications for petrogenesis and tectonic setting of highly evolved, rare-metal enriched granites

USGS Publications Warehouse

du Bray, E.A.

1994-01-01

Compositions and pleochroism of micas in fourteen peraluminous alkali-feldspar granites in the eastern part of the Late Proterozoic Arabian Shield are unlike those of micas (principally biotite) in most calc-alkaline granitoid rocks. Compositions of these micas are distinguished by elevated abundances of Li2O, F, and numerous cations and by low MgO abundances. These micas, constituents of highly evolved rare-metal enriched granitoids, represent an iron-lithium substitution series that ranges from lithium-poor siderophyllite to lithium-rich ferroan lepidolite. The eastern Arabian Shield also hosts six epizonal granitoids that contain colorless micas. Compositions of these micas, mostly muscovite, and their host granitoids are distinct from those of the iron-lithium micas and their host granitoids. Compositions of the analyzed micas have a number of petrogenetic implications. The twenty granitoids containing these micas form three compositional groups that reflect genesis in particular tectonic regimes; mica compositions define the same three groups. The presence of magmatic muscovite in six of these shallowly crystallized granitoids conflicts with experimental data indicating muscovite stability at pressures greater than 3 kbar. Muscovite in the Arabian granitoids probably results from its non-ideal composition; the presence of muscovite cannot be used as a pressure indicator. Finally, mineral/matrix partition coefficients are significantly greater than 1.0 for a number of cations, the rare-earth elements in particular, in many of the analyzed iron-lithium micas. Involvement of these types of micas in partial melting or fractionation processes can have a major influence on silicate liquid compositions. ?? 1994 Springer-Verlag.

Catalytic and inhibiting effects of lithium peroxide and hydroxide on sodium chlorate decomposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cannon, J.C.; Zhang, Y.

1995-09-01

Chemical oxygen generators based on sodium chlorate and lithium perchlorate are used in airplanes, submarines, diving, and mine rescue. Catalytic decomposition of sodium chlorate in the presence of cobalt oxide, lithium peroxide, and lithium hydroxide is studied using thermal gravimetric analysis. Lithium peroxide and hydroxide are both moderately active catalysts for the decomposition of sodium chlorate when used alone, and inhibitors when used with the more active catalyst cobalt oxide.

Quasi-phase-matched second-harmonic generation of 532 nm radiation in 25 degrees -rotated, x-cut, near-stoichiometric, lithium tantalate fabricated by vapor transport equilibration.

PubMed

Hum, D S; Route, R K; Fejer, M M

2007-04-15

Quasi-phase-matched second-harmonic generation of 532 nm radiation in 25 degrees -rotated, x-cut, near-stoichiometric lithium tantalate has been performed. Using a face-normal topology for frequency conversion applications allows scalable surface area to avoid surface and volume damage in high-power interactions. First-order, quasi-phase-matched second-harmonic generation was achieved using near-stoichiometric lithium tantalate fabricated by vapor transport equilibration. These crystals supported 1 J of 1064 nm radiation and generated 21 mJ of 532 nm radiation from a 7 ns, Q-switched Nd:YAG laser within a factor of 4.2 of expectation.

Redox potential trend with transition metal elements in lithium-ion battery cathode materials

NASA Astrophysics Data System (ADS)

Chen, Zhenlian; Li, Jun

2013-03-01

First-principles calculations are performed to investigate the relationship between the intrinsic voltage and element-lattice for the popular transition metal oxides and polyoxyanionic compounds as cathode materials for lithium-ion batteries. A V-shape redox potential in olivine phosphates LiMPO4 and orthogonal silicates Li2MSiO4 (M =Mn, Fe, Co, Ni), and an N-shape one in layered oxides LiMO2 (M =Mn, Fe, Co, Ni, Cu) relative to transition metal M elements are found to be inversely characteristic of electronic energy contribution, which costs energy in the lithiation process and is defined as electron affinity. The maxima of electron affinity, locating at different elements for different types of crystal lattices are determined by delectronic configurations that cross the turning point of a full occupancy of electronic bands, which is determined by the cooperative effect of crystal field splitting and intraionic exchange interactions. The Ningbo Key Innovation Team, National Natural Science Foundation of China, Postdoctoral Foundation of China

Microstructure of ultra high performance concrete containing lithium slag.

PubMed

He, Zhi-Hai; Du, Shi-Gui; Chen, Deng

2018-04-03

Lithium slag (LS) is discharged as a byproduct in the process of the lithium carbonate, and it is very urgent to explore an efficient way to recycle LS in order to protect the environments and save resources. Many available supplementary cementitious materials for partial replacement of cement and/or silica fume (SF) can be used to prepare ultra high performance concrete (UHPC). The effect of LS to replace SF partially by weight used as a supplementary cementitious material (0%, 5%, 10% and 15% of binder) on the compressive strengths and microstructure evolution of UHPC has experimentally been studied by multi-techniques including mercury intrusion porosimetry, scanning electron microscope and nanoindentation technique. The results show that the use of LS degrades the microstructure of UHPC at early ages, and however, the use of LS with the appropriate content improves microstructure of UHPC at later ages. The hydration products of UHPC are mainly dominated by ultra-high density calcium-silicate-hydrate (UHD C-S-H) and interfacial transition zone (ITZ) in UHPC has similar compact microstructure with the matrix. The use of LS improves the hydration degree of UHPC and increases the elastic modulus of ITZ in UHPC. LS is a promising substitute for SF for preparation UHPC. Copyright © 2018 Elsevier B.V. All rights reserved.

An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes

PubMed Central

Zhao, Chen-Zi; Zhang, Xue-Qiang; Cheng, Xin-Bing; Zhang, Rui; Xu, Rui; Chen, Peng-Yu; Peng, Hong-Jie; Huang, Jia-Qi

2017-01-01

Lithium metal is strongly regarded as a promising electrode material in next-generation rechargeable batteries due to its extremely high theoretical specific capacity and lowest reduction potential. However, the safety issue and short lifespan induced by uncontrolled dendrite growth have hindered the practical applications of lithium metal anodes. Hence, we propose a flexible anion-immobilized ceramic–polymer composite electrolyte to inhibit lithium dendrites and construct safe batteries. Anions in the composite electrolyte are tethered by a polymer matrix and ceramic fillers, inducing a uniform distribution of space charges and lithium ions that contributes to a dendrite-free lithium deposition. The dissociation of anions and lithium ions also helps to reduce the polymer crystallinity, rendering stable and fast transportation of lithium ions. Ceramic fillers in the electrolyte extend the electrochemically stable window to as wide as 5.5 V and provide a barrier to short circuiting for realizing safe batteries at elevated temperature. The anion-immobilized electrolyte can be applied in all–solid-state batteries and exhibits a small polarization of 15 mV. Cooperated with LiFePO4 and LiNi0.5Co0.2Mn0.3O2 cathodes, the all–solid-state lithium metal batteries render excellent specific capacities of above 150 mAh⋅g−1 and well withstand mechanical bending. These results reveal a promising opportunity for safe and flexible next-generation lithium metal batteries. PMID:28973945

High-flux neutron source based on a liquid-lithium target

NASA Astrophysics Data System (ADS)

Halfon, S.; Feinberg, G.; Paul, M.; Arenshtam, A.; Berkovits, D.; Kijel, D.; Nagler, A.; Eliyahu, I.; Silverman, I.

2013-04-01

A prototype compact Liquid Lithium Target (LiLiT), able to constitute an accelerator-based intense neutron source, was built. The neutron source is intended for nuclear astrophysical research, boron neutron capture therapy (BNCT) in hospitals and material studies for fusion reactors. The LiLiT setup is presently being commissioned at Soreq Nuclear research Center (SNRC). The lithium target will produce neutrons through the 7Li(p,n)7Be reaction and it will overcome the major problem of removing the thermal power generated by a high-intensity proton beam, necessary for intense neutron flux for the above applications. The liquid-lithium loop of LiLiT is designed to generate a stable lithium jet at high velocity on a concave supporting wall with free surface toward the incident proton beam (up to 10 kW). During off-line tests, liquid lithium was flown through the loop and generated a stable jet at velocity higher than 5 m/s on the concave supporting wall. The target is now under extensive test program using a high-power electron-gun. Up to 2 kW electron beam was applied on the lithium flow at velocity of 4 m/s without any flow instabilities or excessive evaporation. High-intensity proton beam irradiation will take place at SARAF (Soreq Applied Research Accelerator Facility) superconducting linear accelerator currently in commissioning at SNRC.

Fracture Strength of Monolithic All-Ceramic Crowns on Titanium Implant Abutments.

PubMed

Weyhrauch, Michael; Igiel, Christopher; Scheller, Herbert; Weibrich, Gernot; Lehmann, Karl Martin

2016-01-01

The fracture strengths of all-ceramic crowns cemented on titanium implant abutments may vary depending on crown materials and luting agents. The purpose of this study was to examine differences in fracture strength among crowns cemented on implant abutments using crowns made of seven different monolithic ceramic materials and five different luting agents. In total, 525 crowns (75 each of Vita Mark II, feldspathic ceramic [FSC]; Ivoclar Empress CAD, leucite-reinforced glass ceramic [LrGC]; Ivoclar e.max CAD, lithium disilicate [LiDS]; Vita Suprinity, presintered zirconia-reinforced lithium silicate ceramic [PSZirLS]; Vita Enamic, polymer-reinforced fine-structure feldspathic ceramic [PolyFSP], Lava Ultimate; resin nanoceramic [ResNC], Celtra Duo; fully crystallized zirconia-reinforced lithium silicate [FcZirLS]) were milled using a CAD/CAM system. The inner surfaces of the crowns were etched and silanized. Titanium implant abutments were fixed on implant analogs, and airborne-particle abrasion was used on their exterior specific adhesion surfaces (Al2O3, 50 μm). Then, the abutments were degreased and silanized. The crowns were cemented on the implant abutments using five luting agents (Multilink Implant, Variolink II, RelyX Unicem, GC FujiCEM, Panavia 2.0). After thermocycling for 5,000 cycles (5 to 55°C, 30 seconds dwell time), the crowns were subjected to fracture strength testing under static load using a universal testing machine. Statistical analyses were performed using analysis of variance (α = .0002) and the Bonferroni correction. No significant difference among the luting agents was found using the different all-ceramic materials. Ceramic materials LiDS, PSZirLS, PolyFSP, and ResNC showed significantly higher fracture strength values compared with FSC, FcZirLS, and LrGC. The PSZirLS especially showed significantly better results. Within the limitations of this study, fracture strength was not differentially affected by the various luting agents. However, the fracture strength was significantly higher for PSZirLS, PolyFSP, ResNC, and LiDS ceramics than for the FSP, LrGC, and the FcZirLS ceramic with all luting agents tested.

Development of a space stable thermal control coatings for use in large space vehicles

NASA Technical Reports Server (NTRS)

Gilligan, J. E.; Ashford, N. A.; Harada, Y.; Leas, R. M.

1971-01-01

The preparation and evaluation of zinc orthotitanate and of several new pigments and the environmental testing and evaluation of these pigments and of coatings made from them constitute the bulk of the work accomplished. New pigments were prepared and EPR spectra of pigments and their precursor compounds studied. Results of extensive testing of commercially-available, strippable, protective coatings are reported; Owens-Illinois 650 glass resin has been stabilized against progressive mechanical failures; and definite improvements have been noted. A zinc oxide pigmented lithium silicate paint has demonstrated very good ultraviolet stability.

Exploration of the Feasibility of Present Generation Lithium Batteries for Electric Vehicles.

DTIC Science & Technology

1982-11-01

would allow for overcharging the battery as a whole. Chemical redox pairs with formal potentials above the cathode potential and below the potential...AD-A 24 098 EXPLORATION 0F THE FEASIBILT 0F PRESENT GENERATION 1/ LITHIUM BATTERIES FOR ELECTRIC VEHICLES(U) EIC LABS INC NEWTON MA P B HARRIS ET AL...LITHIUM BATTERIES FOR ELECTRIC VEHICLES by P. B. Harris, G. L. Holleck, J. Buzby, J. Avery, L. Pitts and K. M. Abraham EIC Laboratories, Inc. 67 Chapel

Design of pseudorandom binary sequence generator using lithium-niobate-based Mach-Zehnder interferometers

NASA Astrophysics Data System (ADS)

Choudhary, Kuldeep; Kumar, Santosh

2017-05-01

The application of electro-optic effect in lithium-niobate-based Mach-Zehnder interferometer to design a 3-bit optical pseudorandom binary sequence (PRBS) generator has been proposed, which is characterized by its simplicity of generation and stability. The proposed device is optoelectronic in nature. The PBRS generator is immensely applicable for pattern generation, encryption, and coding applications in optical networks. The study is carried out by simulating the proposed device with beam propagation method.

Financial Summary, Nanofiltration Data, and Lithium Uptake Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jay Renew

Integrated testing of nanofiltration and lithium uptake subsystems using synthetic geothermal brine. Also includes a financial summary (Pro Forma) of the proposed 'Geothermal Thermoelectric Generation (G-TEG) with Integrated Temperature Driven Membrane Distillation and Novel Manganese Oxide for Lithium Extraction' (first pass 500 gpm).

Rapid determination of nanogram amounts of tellurium in silicate rocks

USGS Publications Warehouse

Greenland, L.P.; Campbell, E.Y.

1976-01-01

A hydride-generation flameless atomic-absorption technique is used to determine as little as 5 ng g-1 tellurium in 0.25 g of silicate rock. After acid decomposition of the sample, tellurium hydride is generated with sodium borohydride and the vapor passed directly to a resistance-heated quartz cell mounted in an atomic-absorption spectrophotometer. Analyses of 11 U.S. Geological Survey standard rocks are presented. ?? 1976.

Lithium isotope behaviour during weathering in the Ganges Alluvial Plain

NASA Astrophysics Data System (ADS)

Pogge von Strandmann, Philip A. E.; Frings, Patrick J.; Murphy, Melissa J.

2017-02-01

The Ganges river system is responsible for the transportation of a large flux of dissolved materials derived from Himalayan weathering to the oceans. Silicate weathering-driven cooling resulting from uplift of the Himalayas has been proposed to be a key player in Cenozoic climate variation. This study has analysed Li isotope (δ7Li) ratios from over 50 Ganges river waters and sediments, in order to trace silicate weathering processes. Sediments have δ7Li of ∼0‰, identical to bulk continental crust, however suspended sediment depth profiles do not display variations associated with grain size that have been observed in other large river systems. Dissolved δ7Li are low (∼11‰) in the Ganges headwaters, but reach a constant value of 21 ± 1.6‰ within a relatively short distance downstream, which is then maintained for almost 2000 km to the Ganges mouth. Given that Li isotopes are controlled by the ratio of primary mineral dissolution to secondary mineral formation, this suggests that the Ganges floodplain is at steady-state in terms of these processes for most of its length. Low δ7Li in the mountainous regions suggest silicate weathering is therefore at its most congruent where uplift and fresh silicate exposure rates are high. However, there is no correlation between δ7Li and the silicate weathering rate in these rivers, suggesting that Li isotopes cannot be used as a weathering-rate tracer, although they do inform on weathering congruency and intensity. The close-to-constant δ7Li values for the final 2000 km of Ganges flow also suggest that once the size of the alluvial plain reached more than ∼500 km (the flow distance after which riverine δ7Li stops varying), the Ganges exerted little influence on the changing Cenozoic seawater δ7Li, because riverine δ7Li attained a near steady-state composition.

Infrared thermography non-destructive evaluation of lithium-ion battery

NASA Astrophysics Data System (ADS)

Wang, Zi-jun; Li, Zhi-qiang; Liu, Qiang

2011-08-01

The power lithium-ion battery with its high specific energy, high theoretical capacity and good cycle-life is a prime candidate as a power source for electric vehicles (EVs) and hybrid electric vehicles (HEVs). Safety is especially important for large-scale lithium-ion batteries, especially the thermal analysis is essential for their development and design. Thermal modeling is an effective way to understand the thermal behavior of the lithium-ion battery during charging and discharging. With the charging and discharging, the internal heat generation of the lithium-ion battery becomes large, and the temperature rises leading to an uneven temperature distribution induces partial degradation. Infrared (IR) Non-destructive Evaluation (NDE) has been well developed for decades years in materials, structures, and aircraft. Most thermographic methods need thermal excitation to the measurement structures. In NDE of battery, the thermal excitation is the heat generated from carbon and cobalt electrodes in electrolyte. A technique named "power function" has been developed to determine the heat by chemical reactions. In this paper, the simulations of the transient response of the temperature distribution in the lithium-ion battery are developed. The key to resolving the security problem lies in the thermal controlling, including the heat generation and the internal and external heat transfer. Therefore, three-dimensional modelling for capturing geometrical thermal effects on battery thermal abuse behaviour is required. The simulation model contains the heat generation during electrolyte decomposition and electrical resistance component. Oven tests are simulated by three-dimensional model and the discharge test preformed by test system. Infrared thermography of discharge is recorded in order to analyze the security of the lithium-ion power battery. Nondestructive detection is performed for thermal abuse analysis and discharge analysis.

Clinical assessment of pacemaker power sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bilitch, M.; Parsonnet, V.; Furman, S.

1980-01-01

The development of power sources for cardiac pacemakers has progressed from a 15-year usage of mercury-zinc batteries to widely used and accepted lithium cells. At present, there are about 6 different types of lithium cells incorporated into commercially distributed pacemakers. The authors reviewed experience over a 5-year period with 1711 mercury-zinc, 130 nuclear (P238) and 1912 lithium powered pacemakers. The lithium units have included 698 lithium-iodide, 270 lithium-silver chromate, 135 lithium-thionyl chloride, 31 lithium-lead and 353 lithium-cupric sulfide batteries. 57 of the lithium units have failed (91.2% component failure and 5.3% battery failure). 459 mercury-zinc units failed (25% component failuremore » and 68% battery depletion). The data show that lithium powered pacemaker failures are primarily component, while mercury-zinc failures are primarily battery related. It is concluded that mercury-zinc powered pulse generators are obsolete and that lithium and nuclear (P238) power sources are highly reliable over the 5 years for which data are available. 3 refs.« less

A sulfur host based on titanium monoxide@carbon hollow spheres for advanced lithium–sulfur batteries

PubMed Central

Li, Zhen; Zhang, Jintao; Guan, Buyuan; Wang, Da; Liu, Li-Min; Lou, Xiong Wen (David)

2016-01-01

Lithium–sulfur batteries show advantages for next-generation electrical energy storage due to their high energy density and cost effectiveness. Enhancing the conductivity of the sulfur cathode and moderating the dissolution of lithium polysulfides are two key factors for the success of lithium–sulfur batteries. Here we report a sulfur host that overcomes both obstacles at once. With inherent metallic conductivity and strong adsorption capability for lithium-polysulfides, titanium monoxide@carbon hollow nanospheres can not only generate sufficient electrical contact to the insulating sulfur for high capacity, but also effectively confine lithium-polysulfides for prolonged cycle life. Additionally, the designed composite cathode further maximizes the lithium-polysulfide restriction capability by using the polar shells to prevent their outward diffusion, which avoids the need for chemically bonding all lithium-polysulfides on the surfaces of polar particles. PMID:27762261

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1990-01-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Fabrication of ultrathin solid electrolyte membranes of β-Li 3PS 4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

DOE PAGES

Wang, Hui; Hood, Zachary D.; Xia, Younan; ...

2016-04-25

All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li 3PS 4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreasedmore » to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li 3PS 4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

Fatigue failure load of two resin-bonded zirconia-reinforced lithium silicate glass-ceramics: Effect of ceramic thickness.

PubMed

Monteiro, Jaiane Bandoli; Riquieri, Hilton; Prochnow, Catina; Guilardi, Luís Felipe; Pereira, Gabriel Kalil Rocha; Borges, Alexandre Luiz Souto; de Melo, Renata Marques; Valandro, Luiz Felipe

2018-06-01

To evaluate the effect of ceramic thickness on the fatigue failure load of two zirconia-reinforced lithium silicate (ZLS) glass-ceramics, adhesively cemented to a dentin analogue material. Disc-shaped specimens were allocated into 8 groups (n=25) considering two study factors: ZLS ceramic type (Vita Suprinity - VS; and Celtra Duo - CD), and ceramic thickness (1.0; 1.5; 2.0; and 2.5mm). A trilayer assembly (ϕ=10mm; thickness=3.5mm) was designed to mimic a bonded monolithic restoration. The ceramic discs were etched, silanized and luted (Variolink N) into a dentin analogue material. Fatigue failure load was determined using the Staircase method (100,000 cycles at 20Hz; initial fatigue load ∼60% of the mean monotonic load-to-failure; step size ∼5% of the initial fatigue load). A stainless-steel piston (ϕ=40mm) applied the load into the center of the specimens submerged in water. Fractographic analysis and Finite Element Analysis (FEA) were also performed. The ceramic thickness influenced the fatigue failure load for both ZLS materials: Suprinity (716N up to 1119N); Celtra (404N up to 1126N). FEA showed that decreasing ceramic thickness led to higher stress concentration on the cementing interface. Different ZLS glass-ceramic thicknesses influenced the fatigue failure load of the bonded system (i.e. the thicker the glass ceramic is, the higher the fatigue failure load will be). Different microstructures of the ZLS glass-ceramics might affect the fatigue behavior. FEA showed that the thicker the glass ceramic is, the lower the stress concentration at the tensile surface will be. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

Some developments on ceramic-to-metal and glass-ceramics-to-metal seals and related studies

NASA Astrophysics Data System (ADS)

Kothiyal, G. P.; Goswami, M.; Shrikhande, V. K.

2008-05-01

Seals and coatings based on ceramics and glass-ceramics find numerous applications in different disciplines of science and technology including space, accelerators, nuclear energy, chemical industry. Ceramic-to-metal (CM) seals based on conventional design (using brazing alloys) and glass-ceramics have been prepared. While Ag-Cu brazing alloy has been used in conventional CM seal, we have employed lithium zinc silicate (LZS) and lithium aluminum silicate (LAS) glass-ceramics for glass-ceramics-to-metal (GCM) seals. LZS glass-ceramics based on two different compositions; (a) LZSL composition (wt.%)- Li2O: 12.65, ZnO: 1.85, SiO2: 74.4, Al2O3: 3.8, K2O: 2.95, P2O5: 3.15, and B2O3: 1.2 (low ZnO) and (b) LZSH composition (wt.%)- Li2O: 8.9, ZnO: 24.03, SiO2: 53.7, Na2O: 5.42, P2O5: 2.95, and B2O3: 5.0 (high ZnO) were prepared with desired sealing characteristics for matched type seals. In addition, (wt.%) 12.6Li2O-71.7SiO2-5.1Al2O3-4.9K2O-3.2B2O3-2.5P2O5 (LAS-GC) was investigated for compressive type of seal. LZS glass-ceramics-to-Cu as well as SS-321 seals were found to withstand a vacuum of 10-6 Torr with leak rate 10-9 Torr. 1/s and LAS GC-to-SS304 seal showed high pressure endurance of 12000psi. In order to understand the mechanism of sealing, glass-ceramics-to-metal interface study has also been carried out.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

PubMed Central

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-01-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron–hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries. PMID:28393912

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-04-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries.

PubMed

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P; Armand, Michel; Zaghib, Karim

2017-04-10

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Lithium-Based High Energy Density Flow Batteries

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); West, William C. (Inventor); Kindler, Andrew (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Stabilized Lithium-Metal Surface in a Polysulfide-Rich Environment of Lithium-Sulfur Batteries.

PubMed

Zu, Chenxi; Manthiram, Arumugam

2014-08-07

Lithium-metal anode degradation is one of the major challenges of lithium-sulfur (Li-S) batteries, hindering their practical utility as next-generation rechargeable battery chemistry. The polysulfide migration and shuttling associated with Li-S batteries can induce heterogeneities of the lithium-metal surface because it causes passivation by bulk insulating Li2S particles/electrolyte decomposition products on a lithium-metal surface. This promotes lithium dendrite formation and leads to poor lithium cycling efficiency with complicated lithium surface chemistry. Here, we show copper acetate as a surface stabilizer for lithium metal in a polysulfide-rich environment of Li-S batteries. The lithium surface is protected from parasitic reactions with the organic electrolyte and the migrating polysulfides by an in situ chemical formation of a passivation film consisting of mainly Li2S/Li2S2/CuS/Cu2S and electrolyte decomposition products. This passivation film also suppresses lithium dendrite formation by controlling the lithium deposition sites, leading to a stabilized lithium surface characterized by a dendrite-free morphology and improved surface chemistry.

Silicon Anode Consortium | Transportation Research | NREL

Science.gov Websites

Stabilization, Second Quarter Progress Report 2018 Next Generation Anodes for Lithium-Ion Batteries, Second 2018 Next Generation Anodes for Lithium-Ion Batteries, First Quarter Progress Report 2018 Contact For consortium focuses on understanding and eliminating barriers to implementing silicon-based anodes in Li-ion

Thermal modeling of the lithium/polymer battery

NASA Astrophysics Data System (ADS)

Pals, C. R.

1994-10-01

Research in the area of advanced batteries for electric-vehicle applications has increased steadily since the 1990 zero-emission-vehicle mandate of the California Air Resources Board. Due to their design flexibility and potentially high energy and power densities, lithium/polymer batteries are an emerging technology for electric-vehicle applications. Thermal modeling of lithium/polymer batteries is particularly important because the transport properties of the system depend exponentially on temperature. Two models have been presented for assessment of the thermal behavior of lithium/polymer batteries. The one-cell model predicts the cell potential, the concentration profiles, and the heat-generation rate during discharge. The cell-stack model predicts temperature profiles and heat transfer limitations of the battery. Due to the variation of ionic conductivity and salt diffusion coefficient with temperature, the performance of the lithium/polymer battery is greatly affected by temperature. Because of this variation, it is important to optimize the cell operating temperature and design a thermal management system for the battery. Since the thermal conductivity of the polymer electrolyte is very low, heat is not easily conducted in the direction perpendicular to cell layers. Temperature profiles in the cells are not as significant as expected because heat-generation rates in warmer areas of the cell stack are lower than heat-generation rates in cooler areas of the stack. This nonuniform heat-generation rate flattens the temperature profile. Temperature profiles as calculated by this model are not as steep as those calculated by previous models that assume a uniform heat-generation rate.

Organic or organometallic template mediated clay synthesis

DOEpatents

Gregar, Kathleen C.; Winans, Randall E.; Botto, Robert E.

1994-01-01

A method for incorporating diverse Varieties of intercalants or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalant or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

Organic or organometallic template mediated clay synthesis

DOEpatents

Gregar, K.C.; Winans, R.E.; Botto, R.E.

1994-05-03

A method is described for incorporating diverse varieties of intercalates or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalate or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalates or templates may be introduced. The intercalates or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays. 22 figures.

Atom probe tomography of lithium-doped network glasses.

PubMed

Greiwe, Gerd-Hendrik; Balogh, Zoltan; Schmitz, Guido

2014-06-01

Li-doped silicate and borate glasses are electronically insulating, but provide considerable ionic conductivity. Under measurement conditions of laser-assisted atom probe tomography, mobile Li ions are redistributed in response to high electric fields. In consequence, the direct interpretation of measured composition profiles is prevented. It is demonstrated that composition profiles are nevertheless well understood by a complex model taking into account the electronic structure of dielectric materials, ionic mobility and field screening. Quantitative data on band bending and field penetration during measurement are derived which are important in understanding laser-assisted atom probe tomography of dielectric materials. Copyright © 2014 Elsevier B.V. All rights reserved.

Generation of tunable narrow-band surface-emitted terahertz radiation in periodically poled lithium niobate.

PubMed

Weiss, C; Torosyan, G; Avetisyan, Y; Beigang, R

2001-04-15

Generation of tunable narrow-band terahertz (THz) radiation perpendicular to the surface of periodically poled lithium niobate by optical rectification of femtosecond pulses is reported. The generated THz radiation can be tuned by use of different poling periods and different observation angles, limited only by the available bandwidth of the pump pulse. Typical bandwidths were 50-100 GHz, depending on the collection angle and the number of periods involved.

Whispering gallery mode lithium niobate microresonators for photonics applications

NASA Astrophysics Data System (ADS)

Maleki, Lute; Savchenkov, Anatoliy A.; Ilchenko, Vladimir S.; Matsko, Andrey B.

2003-07-01

We review various photonics applications of whispering gallery mode (WGM) dielectric resonators and focus on the capability of generating trains of short optical pulses using WGM lithium niobate cavities. We introduce schemes of optical frequency comb generators, actively mode-locked lasers, and coupled opto-electronic oscillators where WGM cavities are utilized for the light amplification and modulation.

Rapid high-silica magma generation in basalt-dominated rift settings

NASA Astrophysics Data System (ADS)

Berg, Sylvia E.; Troll, Valentin R.; Burchardt, Steffi; Deegan, Frances M.; Riishuus, Morten S.; Whitehouse, Martin J.; Harris, Chris; Freda, Carmela; Ellis, Ben S.; Krumbholz, Michael; Gústafsson, Ludvik E.

2015-04-01

The processes that drive large-scale silicic magmatism in basalt-dominated provinces have been widely debated for decades, with Iceland being at the centre of this discussion [1-5]. Iceland hosts large accumulations of silicic rocks in a largely basaltic oceanic setting that is considered by some workers to resemble the situation documented for the Hadean [6-7]. We have investigated the time scales and processes of silicic volcanism in the largest complete pulse of Neogene rift-related silicic magmatism preserved in Iceland (>450 km3), which is a potential analogue of initial continent nucleation in early Earth. Borgarfjörður Eystri in NE-Iceland hosts silicic rocks in excess of 20 vol.%, which exceeds the ≤12 vol% usual for Iceland [3,8]. New SIMS zircon ages document that the dominantly explosive silicic pulse was generated within a ≤2 Myr window (13.5 ± 0.2 to 12.2 ± 03 Ma), and sub-mantle zircon δ18O values (1.2 to 4.5 ± 0.2‰, n=337) indicate ≤33% assimilation of low-δ18O hydrothermally-altered crust (δ18O=0‰), with intense crustal melting at 12.5 Ma, followed by rapid termination of silicic magma production once crustal fertility declined [9]. This silicic outburst was likely caused by extensive rift flank volcanism due to a rift relocation and a flare of the Iceland plume [4,10] that triggered large-scale crustal melting and generated mixed-origin silicic melts. High-silica melt production from a basaltic parent was replicated in a set of new partial melting experiments of regional hydrated basalts, conducted at 800-900°C and 150 MPa, that produced silicic melt pockets up to 77 wt.% SiO2. Moreover, Ti-in-zircon thermometry from Borgarfjörður Eystri give a zircon crystallisation temperature ~713°C (Ti range from 2.4 to 22.1 ppm, average=7.7 ppm, n=142), which is lower than recorded elsewhere in Iceland [11], but closely overlaps with the zircon crystallisation temperatures documented for Hadean zircon populations [11-13], hinting at crustal recycling as a key process. Our results therefore provide a mechanism and a time-scale for rapid, voluminous silicic magma generation in modern and ancient basalt-dominated rift setting, such as Afar, Taupo, and potentially early Earth. The Neogene plume-related rift flank setting of NE-Iceland may thus constitute a plausible geodynamic and compositional analogue for generating silicic (continental) crust in the subduction-free setting of a young Earth (e.g. ≥3 Ga [14]). [1] Bunsen, R. 1851. Ann. Phys. Chem. 159, 197-272. [2] MacDonald R., et al., 1987. Mineral. Mag. 51, 183-202. [3] Jonasson, K., 2007. J. Geodyn. 43, 101-117. [4] Martin, E., et al., 2011. Earth Planet. Sci. Lett. 311, 28-38. [5] Charreteur, G., et al., 2013.Contrib. Mineral. Petr. 166, 471- 490. [6] Willbold, E., et al., 2009. Earth Planet. Sci. Lett. 279, 44-52. [7] Reimink, J.R., et al., 2014. Nat. Geosci. 7, 529-533. [8] Gústafsson, L.E., et al., 1989. Jökull 39, 75-89. [9] Meade, F.C., et al., 2014. Nat. comm. 5. [10] Óskarsson, B.V., Riishuus, M.S., 2013. J. Volcanol. Geoth. Res. 267, 92-118. [11] Carley, T.L., et al., 2014. Earth Planet. Sci. Lett. 405, 85-97. [12] Trail, D., et al., 2007. Geochem. Geophys. Geosyst.8, Q06014. [13] Harrison, T.M. et al., 2008. Earth Planet. Sci. Lett.268, 476-486. [14] Kamber, B. S., et al., 2005. Earth Planet. Sci. Lett. 240, 276-290.

Complex Diffusion Mechanisms for Li in Feldspar: Re-thinking Li-in-Plag Geospeedometry

NASA Astrophysics Data System (ADS)

Holycross, M.; Watson, E. B.

2017-12-01

In recent years, the lithium isotope system has been applied to model processes in a wide variety of terrestrial environments. In igneous settings, Li diffusion gradients have been frequently used to time heating episodes. Lithium partitioning behavior during decompression or cooling events drives Li transfer between phases, but the extent of Li exchange may be limited by its diffusion rate in geologic materials. Lithium is an exceptionally fast diffuser in silicate media, making it uniquely suited to record short-lived volcanic phenomena. The Li-in-plagioclase geospeedometer is often used to time explosive eruptions by applying laboratory-calibrated Li diffusion coefficients to model concentration profiles in magmatic feldspar samples. To quantify Li transport in natural scenarios, experimental measurements are needed that account for changing temperature and oxygen fugacity as well as different feldspar compositions and crystallographic orientation. Ambient pressure experiments were run at RPI to diffuse Li from a powdered spodumene source into polished sanidine, albite, oligoclase or anorthite crystals over the temperature range 500-950 ºC. The resulting 7Li concentration gradients developed in the mineral specimens were evaluated using laser ablation ICP-MS. The new data show that Li diffusion in all feldspar compositions simultaneously operates by both a "fast" and "slow" diffusion mechanism. Fast path diffusivities are similar to those found by Giletti and Shanahan [1997] for Li diffusion in plagioclase and are typically 10 to 20 times greater than slow path diffusivities. Lithium concentration gradients in the feldspar experiments plot in the shape of two superimposed error function curves with the slow diffusion regime in the near-surface of the crystal. Lithium diffusion is most sluggish in sanidine and is significantly faster in the plagioclase feldspars. It is still unclear what diffusion mechanism operates in nature, but the new measurements may impact how Li-in-plagioclase geospeedometry is used to time igneous processes. Giletti, B.J., and T.M. Shanahan (1997) Alkali diffusion in plagioclase feldspar, Chem. Geol., 139, 3-20

Conductive Polymer Binder-Enabled SiO–Sn xCo yC z Anode for High-Energy Lithium-Ion Batteries

DOE PAGES

Zhao, Hui; Fu, Yanbao; Ling, Min; ...

2016-05-10

In this paper, a SiOSnCoC composite anode is assembled using a conductive polymer binder for the application in next-generation high energy density lithium-ion batteries. A specific capacity of 700 mAh/g is achieved at a 1C (900 mA/g) rate. A high active material loading anode with an areal capacity of 3.5 mAh/cm 2 is demonstrated by mixing SiOSnCoC with graphite. To compensate for the lithium loss in the first cycle, stabilized lithium metal powder (SLMP) is used for prelithiation; when paired with a commercial cathode, a stable full cell cycling performance with a 86% first cycle efficiency is realized. Finally, bymore » achieving these important metrics toward a practical application, this conductive polymer binder/SiOSnCoC anode system presents great promise to enable the next generation of high-energy lithium-ion batteries.« less

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-01-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density (i sub o) values being greater than 60mA sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent (compared to H2) for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed tha basis for the lithium oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-12-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density (i sub o) values being greater than 60mA sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent (compared to H2) for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed tha basis for the lithium oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Synthesis of Ultrathin Si Nanosheets from Natural Clays for Lithium-Ion Battery Anodes.

PubMed

Ryu, Jaegeon; Hong, Dongki; Choi, Sinho; Park, Soojin

2016-02-23

Two-dimensional Si nanosheets have been studied as a promising candidate for lithium-ion battery anode materials. However, Si nanosheets reported so far showed poor cycling performances and required further improvements. In this work, we utilize inexpensive natural clays for preparing high quality Si nanosheets via a one-step simultaneous molten salt-induced exfoliation and chemical reduction process. This approach produces high purity mesoporous Si nanosheets in high yield. As a control experiment, two-step process (pre-exfoliated silicate sheets and subsequent chemical reduction) cannot sustain their original two-dimensional structure. In contrast, one-step method results in a production of 5 nm-thick highly porous Si nanosheets. Carbon-coated Si nanosheet anodes exhibit a high reversible capacity of 865 mAh g(-1) at 1.0 A g(-1) with an outstanding capacity retention of 92.3% after 500 cycles. It also delivers high rate capability, corresponding to a capacity of 60% at 20 A g(-1) compared to that of 2.0 A g(-1). Furthermore, the Si nanosheet electrodes show volume expansion of only 42% after 200 cycles.

Lithium enrichment in intracontinental rhyolite magmas leads to Li deposits in caldera basins.

PubMed

Benson, Thomas R; Coble, Matthew A; Rytuba, James J; Mahood, Gail A

2017-08-16

The omnipresence of lithium-ion batteries in mobile electronics, and hybrid and electric vehicles necessitates discovery of new lithium resources to meet rising demand and to diversify the global lithium supply chain. Here we demonstrate that lake sediments preserved within intracontinental rhyolitic calderas formed on eruption and weathering of lithium-enriched magmas have the potential to host large lithium clay deposits. We compare lithium concentrations of magmas formed in a variety of tectonic settings using in situ trace-element measurements of quartz-hosted melt inclusions to demonstrate that moderate to extreme lithium enrichment occurs in magmas that incorporate felsic continental crust. Cenozoic calderas in western North America and in other intracontinental settings that generated such magmas are promising new targets for lithium exploration because lithium leached from the eruptive products by meteoric and hydrothermal fluids becomes concentrated in clays within caldera lake sediments to potentially economically extractable levels.Lithium is increasingly being utilized for modern technology in the form of lithium-ion batteries. Here, using in situ measurements of quartz-hosted melt inclusions, the authors demonstrate that preserved lake sediments within rhyolitic calderas have the potential to host large lithium-rich clay deposits.

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

PubMed Central

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; Zhao, Jie; Yan, Kai; Cui, Yi

2016-01-01

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm−2 in both carbonate and ether electrolyte. The advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes. PMID:26987481

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; ...

2016-03-18

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yayuan; Lin, Dingchang; Liang, Zheng

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Water generation and transport through the high-pressure ice layers of Titan and Ganymede

NASA Astrophysics Data System (ADS)

Kalousova, K.; Sotin, C.; Choblet, G.; Tobie, G.; Grasset, O.

2017-09-01

We investigate the generation and transport of water through the high-pressure (HP) ice layers of Ganymede and Titan using a numerical model of two-phase convection in 2D geometry. Our results suggest that water can be generated at the silicate/HP ice interface for small to intermediate values of Rayleigh number (Ra 1.e8-1.e10) while no melt is generated for the higher values (Ra 1.e11). If generated, water is transported through the layer by the upwelling plumes and, depending on the vigor of convection, it stays liquid (smaller Ra) or it may freeze (intermediate Ra) before melting again as the plume reaches the temperate layer at the interface with the ocean. The thickness of this layer as well as the amount of melt that is extracted from it is controlled by the HP ice permeability. This process may enable the transfer of volatiles and salts that might have been leached from silicates by the meltwater. Since the HP ice layer is much thinner on Titan than on Ganymede, it is probably more permeable for volatiles and salts leached from the silicate core.

Methylated silicates may explain the release of chlorinated methane from Martian soil

NASA Astrophysics Data System (ADS)

Bak, Ebbe N.; Jensen, Svend J. Knak; Nørnberg, Per; Finster, Kai

2016-01-01

The only organic compounds that have been detected in the Martian soil are simple chlorinated compounds released from heated surface material. However, the sources of the organic carbon are in dispute. Wind abraded silicates, which are widespread on the Martian surface, can sequester atmospheric methane which generates methylated silicates and thus could provide a mechanism for accumulation of reduced carbon in the surface soil. In this study we show that thermal volatilization of methylated silicates in the presence of perchlorate leads to the production of chlorinated methane. Thus, methylated silicates could be a source of the organic carbon released as chlorinated methane upon thermal volatilization of Martian soil samples. Further, our experiments show that the ratio of the different chlorinated compounds produced is dependent on the mass ratio of perchlorate to organic carbon in the soil.

Lithium Azide as an Electrolyte Additive for All-Solid-State Lithium-Sulfur Batteries.

PubMed

Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Bondarchuk, Oleksandr; Rodriguez-Martinez, Lide M; Zhang, Heng; Armand, Michel

2017-11-27

Of the various beyond-lithium-ion battery technologies, lithium-sulfur (Li-S) batteries have an appealing theoretical energy density and are being intensely investigated as next-generation rechargeable lithium-metal batteries. However, the stability of the lithium-metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long-term stability of Li-S batteries. Herein, we report lithium azide (LiN 3 ) as a novel electrolyte additive for all-solid-state Li-S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state-of-the-art additive lithium nitrate (LiNO 3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reflection second harmonic generation on a z -cut congruent lithium niobate crystal

NASA Astrophysics Data System (ADS)

Sono, T. J.; Scott, J. G.; Sones, C. L.; Valdivia, C. E.; Mailis, S.; Eason, R. W.; Frey, J. G.; Danos, L.

2006-11-01

Reflection second harmonic generation experiments were performed on z -cut congruent lithium niobate crystals (LiNbO3) to reveal the interfacial layer symmetry as the crystal is rotated around the z axis. To suppress the bulk contribution, the fundamental wavelength was selected to be 532nm , resulting in second harmonic generation at a wavelength within the absorption region of the crystal. The polarity of the direction of the y -axis was determined from second harmonic generation data and used to show that this direction also inverts during domain inversion.

Thermal effects in high-power CW second harmonic generation in Mg-doped stoichiometric lithium tantalate.

PubMed

Tovstonog, Sergey V; Kurimura, Sunao; Suzuki, Ikue; Takeno, Kohei; Moriwaki, Shigenori; Ohmae, Noriaki; Mio, Norikatsu; Katagai, Toshio

2008-07-21

We investigated thermal behaviors of single-pass second-harmonic generation of continuous wave green radiation with high efficiency by quasi-phase matching in periodically poled Mg-doped stoichiometric lithium tantalate (PPMgSLT). Heat generation turned out to be directly related to the green light absorption in the material. Strong relation between an upper limit of the second harmonic power and confocal parameter was found. Single-pass second-harmonic generation of 16.1 W green power was achieved with 17.6% efficiency in Mg:SLT at room temperature.

Determination of total tin in silicate rocks by graphite furnace atomic absorption spectrometry

USGS Publications Warehouse

Elsheimer, H.N.; Fries, T.L.

1990-01-01

A method is described for the determination of total tin in silicate rocks utilizing a graphite furnace atomic absorption spectrometer with a stabilized-temperature platform furnace and Zeeman-effect background correction. The sample is decomposed by lithium metaborate fusion (3 + 1) in graphite crucibles with the melt being dissolved in 7.5% hydrochloric acid. Tin extractions (4 + 1 or 8 + 1) are executed on portions of the acid solutions using a 4% solution of tricotylphosphine oxide in methyl isobutyl ketone (MIBK). Ascorbic acid is added as a reducing agent prior to extraction. A solution of diammonium hydrogenphosphate and magnesium nitrate is used as a matrix modifier in the graphite furnace determination. The limit of detection is > 10 pg, equivalent to > 1 ??g l-1 of tin in the MIBK solution or 0.2-0.3 ??g g-61 in the rock. The concentration range is linear between 2.5 and 500 ??g l-1 tin in solution. The precision, measured as relative standard deviation, is < 20% at the 2.5 ??g l-1 level and < 7% at the 10-30 ??g l-1 level of tin. Excellent agreement with recommended literature values was found when the method was applied to the international silicate rock standards BCR-1, PCC-1, GSP-1, AGV-1, STM-1, JGb-1 and Mica-Fe. Application was made to the determination of tin in geological core samples with total tin concentrations of the order of 1 ??g g-1 or less.

Method for treating beta-spodumene ceramics

DOEpatents

Day, J. Paul; Hickman, David L.

1994-09-27

A vapor-phase method for treating a beta-spodumene ceramic article to achieve a substitution of exchangeable hydrogen ions for the lithium present in the beta-spodumene crystals, wherein a barrier between the ceramic article and the source of exchangeable hydrogen ions is maintained in order to prevent lithium contamination of the hydrogen ion source and to generate highly recoverable lithium salts, is provided.

Direct observation of lithium polysulfides in lithium-sulfur batteries using operando X-ray diffraction

NASA Astrophysics Data System (ADS)

Conder, Joanna; Bouchet, Renaud; Trabesinger, Sigita; Marino, Cyril; Gubler, Lorenz; Villevieille, Claire

2017-06-01

In the on going quest towards lithium-battery chemistries beyond the lithium-ion technology, the lithium-sulfur system is emerging as one of the most promising candidates. The major outstanding challenge on the route to commercialization is controlling the so-called polysulfide shuttle, which is responsible for the poor cycling efficiency of the current generation of lithium-sulfur batteries. However, the mechanistic understanding of the reactions underlying the polysulfide shuttle is still incomplete. Here we report the direct observation of lithium polysulfides in a lithium-sulfur cell during operation by means of operando X-ray diffraction. We identify signatures of polysulfides adsorbed on the surface of a glass-fibre separator and monitor their evolution during cycling. Furthermore, we demonstrate that the adsorption of the polysulfides onto SiO2 can be harnessed for buffering the polysulfide redox shuttle. The use of fumed silica as an electrolyte additive therefore significantly improves the specific charge and Coulombic efficiency of lithium-sulfur batteries.

Improving lithium therapeutics by crystal engineering of novel ionic cocrystals.

PubMed

Smith, Adam J; Kim, Seol-Hee; Duggirala, Naga K; Jin, Jingji; Wojtas, Lukasz; Ehrhart, Jared; Giunta, Brian; Tan, Jun; Zaworotko, Michael J; Shytle, R Douglas

2013-12-02

Current United States Food and Drug Administration (FDA)-approved lithium salts are plagued with a narrow therapeutic window. Recent attempts to find alternative drugs have identified new chemical entities, but lithium's polypharmacological mechanisms for treating neuropsychiatric disorders are highly debated and are not yet matched. Thus, re-engineering current lithium solid forms in order to optimize performance represents a low cost and low risk approach to the desired therapeutic outcome. In this contribution, we employed a crystal engineering strategy to synthesize the first ionic cocrystals (ICCs) of lithium salts with organic anions. We are unaware of any previous studies that have assessed the biological efficacy of any ICCs, and encouragingly we found that the new speciation did not negatively affect established bioactivities of lithium. We also observed that lithium ICCs exhibit modulated pharmacokinetics compared to lithium carbonate. Indeed, the studies detailed herein represent an important advancement in a crystal engineering approach to a new generation of lithium therapeutics.

Two-Dimensional Metal Oxide Nanomaterials for Next-Generation Rechargeable Batteries.

PubMed

Mei, Jun; Liao, Ting; Kou, Liangzhi; Sun, Ziqi

2017-12-01

The exponential increase in research focused on two-dimensional (2D) metal oxides has offered an unprecedented opportunity for their use in energy conversion and storage devices, especially for promising next-generation rechargeable batteries, such as lithium-ion batteries (LIBs) and sodium-ion batteries (NIBs), as well as some post-lithium batteries, including lithium-sulfur batteries, lithium-air batteries, etc. The introduction of well-designed 2D metal oxide nanomaterials into next-generation rechargeable batteries has significantly enhanced the performance of these energy-storage devices by providing higher chemically active interfaces, shortened ion-diffusion lengths, and improved in-plane carrier-/charge-transport kinetics, which have greatly promoted the development of nanotechnology and the practical application of rechargeable batteries. Here, the recent progress in the application of 2D metal oxide nanomaterials in a series of rechargeable LIBs, NIBs, and other post lithium-ion batteries is reviewed relatively comprehensively. Current opportunities and future challenges for the application of 2D nanomaterials in energy-storage devices to achieve high energy density, high power density, stable cyclability, etc. are summarized and outlined. It is believed that the integration of 2D metal oxide nanomaterials in these clean energy devices offers great opportunities to address challenges driven by increasing global energy demands. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-phase convection in Ganymede's high-pressure ice layer - Implications for its geological evolution

NASA Astrophysics Data System (ADS)

Kalousová, Klára; Sotin, Christophe; Choblet, Gaël; Tobie, Gabriel; Grasset, Olivier

2018-01-01

Ganymede, the largest moon in the solar system, has a fully differentiated interior with a layer of high-pressure (HP) ice between its deep ocean and silicate mantle. In this paper, we study the dynamics of this layer using a numerical model of two-phase ice-water mixture in two-dimensional Cartesian geometry. While focusing on the generation of water at the silicate/HP ice interface and its upward migration towards the ocean, we investigate the effect of bottom heat flux, the layer thickness, and the HP ice viscosity and permeability. Our results suggest that melt can be generated at the silicate/HP ice interface for small layer thickness ( ≲ 200 km) and high values of heat flux ( ≳ 20 mW m-2) and viscosity ( ≳ 1015 Pa s). Once generated, the water is transported through the layer by the upwelling plumes. Depending on the vigor of convection, it stays liquid or it may freeze before melting again as the plume reaches the temperate (partially molten) layer at the boundary with the ocean. The thickness of this layer as well as the amount of melt that is extracted from it is controlled by the permeability of the HP ice. This process constitutes a means of transporting volatiles and salts that might have dissolved into the melt present at the silicate/HP ice interface. As the moon cools down, the HP ice layer becomes less permeable because the heat flux from the silicates decreases and the HP ice layer thickens.

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

DOEpatents

Vajda, Stefan; Curtiss, Larry A.; Lu, Jun; Amine, Khalil; Tyo, Eric C.

2016-11-15

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.

Mg-perovskite/silicate melt and magnesiowuestite/silicate melt partition coefficients for KLB-1 at 250 Kbars

NASA Technical Reports Server (NTRS)

Drake, Michael J.; Rubie, David C.; Mcfarlane, Elisabeth A.

1992-01-01

The partitioning of elements amongst lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements was reported previously, and these results as well as interpretations based on them have generated controversy. Here we report what are to our knowledge only the second set of directly measured trace element partition coefficients for a natural system (KLB-1).

High-flux neutron source based on a liquid-lithium target

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halfon, S.; Feinberg, G.; Paul, M.

2013-04-19

A prototype compact Liquid Lithium Target (LiLiT), able to constitute an accelerator-based intense neutron source, was built. The neutron source is intended for nuclear astrophysical research, boron neutron capture therapy (BNCT) in hospitals and material studies for fusion reactors. The LiLiT setup is presently being commissioned at Soreq Nuclear research Center (SNRC). The lithium target will produce neutrons through the {sup 7}Li(p,n){sup 7}Be reaction and it will overcome the major problem of removing the thermal power generated by a high-intensity proton beam, necessary for intense neutron flux for the above applications. The liquid-lithium loop of LiLiT is designed to generatemore » a stable lithium jet at high velocity on a concave supporting wall with free surface toward the incident proton beam (up to 10 kW). During off-line tests, liquid lithium was flown through the loop and generated a stable jet at velocity higher than 5 m/s on the concave supporting wall. The target is now under extensive test program using a high-power electron-gun. Up to 2 kW electron beam was applied on the lithium flow at velocity of 4 m/s without any flow instabilities or excessive evaporation. High-intensity proton beam irradiation will take place at SARAF (Soreq Applied Research Accelerator Facility) superconducting linear accelerator currently in commissioning at SNRC.« less

A design of spectrophotometric microfluidic chip sensor for analyzing silicate in seawater

NASA Astrophysics Data System (ADS)

Cao, X.; Zhang, S. W.; Chu, D. Z.; Wu, N.; Ma, H. K.; Liu, Y.

2017-08-01

High quality and continuous in situ silicate data are required to investigate the mechanism of the biogeochemical cycles and the formation of red tide. There is an urgently growing need for autonomous in situ silicate instruments that perform determination on various platforms. However, due to the high reagents and power consumption, as well as high system complexity leading to low reliability and robustness, the performance of the commercially available silicate sensors is not satisfactory. With these problems, here we present a new generation of microfluidic continuous flow analysis silicate sensor with sufficient analytical performance and robustness, for in situ determination of soluble silicate in seawater. The reaction mechanism of this sensor is based on the reaction of silicate with ammonium molybdate to form a yellow silicomolybdate complex and further reduction to silicomoIybdenum blue by ascorbic acid. The minimum limit of detection was 45.1 nmol L-1, and the linear determination range of the sensor is 0-400 μmol L-1. The recovery rate of the actual water is between 98.1%-104.0%, and the analyzing cycle of the sensor is about 5 minutes. This sensor has the advantages of high accuracy, high integration, low water consumption, and strong anti-interference ability. It has been successfully applied to measuring the silicate in seawater in Jiaozhou Bay.

One-step electrolytic preparation of Si-Fe alloys as anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Hailong; Sun, Diankun; Song, Qiqi; Xie, Wenqi; Jiang, Xu; Zhang, Bo

2016-06-01

One-step electrolytic formation of uniform crystalline Si-Fe alloy particles was successfully demonstrated in direct electro-reduction of solid mixed oxides of SiO2 and Fe2O3 in molten CaCl2 at 900∘C. Upon constant voltage electrolysis of solid mixed oxides at 2.8V between solid oxide cathode and graphite anode for 5h, electrolytic Si-Fe with the same Si/Fe stoichimetry of the precursory oxides was generated. The firstly generated Fe could function as depolarizers to enhance reduction rate of SiO2, resulting in the enhanced reduction kinetics to the electrolysis of individual SiO2. When evaluated as anode for lithium ion batteries, the prepared SiFe electrode showed a reversible lithium storage capacity as high as 470mAh g-1 after 100 cycles at 200mA g-1, promising application in high-performance lithium ion batteries.

Sealing glass-ceramics with near linear thermal strain, Part II: Sequence of crystallization and phase stability

DOE PAGES

Dai, Steve Xunhu; Rodriguez, Mark A.; Griego, James M.

2016-06-01

Here, the sequence of crystallization in a re-crystallizable lithium silicate sealing glass-ceramic Li 2O-SiO 2-Al 2O 3-K 2O-B 2O 3-P 2O 5-ZnO was analyzed by in situ high temperature X-ray diffraction (HTXRD). Glass-ceramic specimens have been subjected to a 2-stage heat treatment schedule, including rapid cooling from sealing temperature to a 1st hold temperature 650 °C, following by heating to a 2nd hold temperature of 810 °C. Notable growth and saturation of Quartz was observed at 650 °C (1st hold).

Electron doping through lithium intercalation to interstitial channels in tetrahedrally bonded SiC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakai, Yuki; Center for Computational Materials, Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, Texas 78712; Oshiyama, Atsushi

2015-11-07

We report on first-principles calculations that clarify the effect of lithium atom intercalation into zinc blende 3C-silicon carbide (3C-SiC) on electronic and structural properties. Lithium atoms inside 3C-SiC are found to donate electrons to 3C-SiC that is an indication of a new way of electron doping through the intercalation. The electrons doped into the conduction band interact with lithium cations and reduce the band spacing between the original valence and conduction bands. We have also found that a silicon monovacancy in 3C-SiC promotes the lithium intercalation, showing that the vacancy generation makes SiC as a possible anode material for lithium-ionmore » battery.« less

An Artificial Lithium Protective Layer that Enables the Use of Acetonitrile-Based Electrolytes in Lithium Metal Batteries.

PubMed

Trinh, Ngoc Duc; Lepage, David; Aymé-Perrot, David; Badia, Antonella; Dollé, Mickael; Rochefort, Dominic

2018-04-23

The resurgence of the lithium metal battery requires innovations in technology, including the use of non-conventional liquid electrolytes. The inherent electrochemical potential of lithium metal (-3.04 V vs. SHE) inevitably limits its use in many solvents, such as acetonitrile, which could provide electrolytes with increased conductivity. The aim of this work is to produce an artificial passivation layer at the lithium metal/electrolyte interface that is electrochemically stable in acetonitrile-based electrolytes. To produce such a stable interface, the lithium metal was immersed in fluoroethylene carbonate (FEC) to generate a passivation layer via the spontaneous decomposition of the solvent. With this passivation layer, the chemical stability of lithium metal is shown for the first time in 1 m LiPF 6 in acetonitrile. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lithium-ion conducting electrolyte salts for lithium batteries.

PubMed

Aravindan, Vanchiappan; Gnanaraj, Joe; Madhavi, Srinivasan; Liu, Hua-Kun

2011-12-16

This paper presents an overview of the various types of lithium salts used to conduct Li(+) ions in electrolyte solutions for lithium rechargeable batteries. More emphasis is paid towards lithium salts and their ionic conductivity in conventional solutions, solid-electrolyte interface (SEI) formation towards carbonaceous anodes and the effect of anions on the aluminium current collector. The physicochemical and functional parameters relevant to electrochemical properties, that is, electrochemical stabilities, are also presented. The new types of lithium salts, such as the bis(oxalato)borate (LiBOB), oxalyldifluoroborate (LiODFB) and fluoroalkylphosphate (LiFAP), are described in detail with their appropriate synthesis procedures, possible decomposition mechanism for SEI formation and prospect of using them in future generation lithium-ion batteries. Finally, the state-of-the-art of the system is given and some interesting strategies for the future developments are illustrated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lithium salts for advanced lithium batteries: Li-metal, Li-O 2, and Li-S

DOE PAGES

Younesi, Reza; Veith, Gabriel M.; Johansson, Patrik; ...

2015-06-01

Presently lithium hexafluorophosphate (LiPF 6) is the dominant Li-salt used in commercial rechargeable lithium-ion batteries (LIBs) based on a graphite anode and a 3-4 V cathode material. While LiPF 6 is not the ideal Li-salt for every important electrolyte property, it has a uniquely suitable combination of properties (temperature range, passivation, conductivity, etc.) rendering it the overall best Li-salt for LIBs. However, this may not necessarily be true for other types of Li-based batteries. Indeed, next generation batteries, for example lithium-metal (Li-metal), lithium-oxygen (Li-O 2), and lithium sulphur (Li-S), require a re-evaluation of Li-salts due to the different electrochemical andmore » chemical reactions and conditions within such cells. Furthermore, this review explores the critical role Li-salts play in ensuring in these batteries viability.« less

Improving Lithium Therapeutics by Crystal Engineering of Novel Ionic Cocrystals

PubMed Central

2013-01-01

Current United States Food and Drug Administration (FDA)-approved lithium salts are plagued with a narrow therapeutic window. Recent attempts to find alternative drugs have identified new chemical entities, but lithium’s polypharmacological mechanisms for treating neuropsychiatric disorders are highly debated and are not yet matched. Thus, re-engineering current lithium solid forms in order to optimize performance represents a low cost and low risk approach to the desired therapeutic outcome. In this contribution, we employed a crystal engineering strategy to synthesize the first ionic cocrystals (ICCs) of lithium salts with organic anions. We are unaware of any previous studies that have assessed the biological efficacy of any ICCs, and encouragingly we found that the new speciation did not negatively affect established bioactivities of lithium. We also observed that lithium ICCs exhibit modulated pharmacokinetics compared to lithium carbonate. Indeed, the studies detailed herein represent an important advancement in a crystal engineering approach to a new generation of lithium therapeutics. PMID:24191685

Synthesis and electrochemical characterization of mesoporous Li2FeSiO4/C composite cathode material for Li-ion batteries

NASA Astrophysics Data System (ADS)

Kumar, Ajay; Jayakumar, O. D.; Bazzi, Khadije; Nazri, Gholam-Abbas; Naik, Vaman M.; Naik, Ratna

2015-03-01

Lithium iron silicate (Li2FeSiO4) has the potential as cathode for Li ion batteries due to its high theoretical capacity (~ 330 mAh/g) and improved safety. The application of Li2FeSiO4 as cathode material has been challenged by its poor electronic conductivity and slow lithium ion diffusion in the solid phase. In order to solve these problems, we have synthesized mesoporous Li2FeSiO4/C composites by sol-gel method using the tri-block copolymer (P123) as carbon source. The phase purity and morphology of the composite materials were characterized by x-ray diffraction, SEM and TEM. The XRD pattern confirmed the formation of ~ 12 nm size Li2FeSiO4 crystallites in composites annealed at 600 °C for 6 h under argon atmosphere. The electrochemical properties are measured using the composite material as positive electrode in a standard coin cell configuration with lithium as the active anode and the cells were tested using AC impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge cycling. The Li2FeSiO4/C composites showed a discharge capacity of ~ 240 mAh/g at a rate of C/30 at room temperature. The effect of different annealing temperature and synthesis time on the electrochemical performance of Li2FeSiO4/C will be presented.

Three-dimensional finite element study on stress generation in synchrotron X-ray tomography reconstructed nickel-manganese-cobalt based half cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Linmin; Xiao, Xianghui; Wen, Youhai

In this study, the stress generation caused by phase transitions and lithium intercalation of nickel-manganese-cobalt (NMC) based half cell with realistic 3D microstructures has been studied using finite element method. The electrochemical properties and discharged curves under various C rates are studied. The potential drops significantly with the increase of C rates. During the discharge process, for particles isolated from the conductive channels, several particles with no lithium ion intercalation are observed. For particles in the electrochemical network, the lithium ion concentration increases during the discharge process. The stress generation inside NMC particles is calculated coupled with lithium diffusion andmore » phase transitions. The results show the stresses near the concave and convex regions are the highest. The neck regions of the connected particles 2 can break and form several isolated particles. If the isolated particles are not connected with the electrically conductive materials such as carbon and binder, the capacity loses in battery. For isolated particles in the conductive channel, cracks are more likely to form on the surface. Moreover, stresses inside the particles increase dramatically when considering phase transitions. The phase transitions introduce an abrupt volume change and generate the strain mismatch, causing the stress increase.« less

On the neutralization of acid rock drainage by carbonate and silicate minerals

NASA Astrophysics Data System (ADS)

Sherlock, E. J.; Lawrence, R. W.; Poulin, R.

1995-02-01

The net result of acid-generating and-neutralizing reactions within mining wastes is termed acid rock drainage (ARD). The oxidation of sulfide minerals is the major contributor to acid generation. Dissolution and alteration of various minerals can contribute to the neutralization of acid. Definitions of alkalinity, acidity, and buffer capacity are reviewed, and a detailed discussion of the dissolution and neutralizing capacity of carbonate and silicate minerals related to equilibium conditions, dissolution mechanism, and kinetics is provided. Factors that determine neutralization rate by carbonate and silicate minerals include: pH, PCO 2, equilibrium conditions, temperature, mineral composition and structure, redox conditions, and the presence of “foreign” ions. Similar factors affect sulfide oxidation. Comparison of rates shows sulfides react fastest, followed by carbonates and silicates. The differences in the reaction mechanisms and kinetics of neutralization have important implications in the prediction, control, and regulation of ARD. Current static and kinetic prediction methods upon which mine permitting, ARD control, and mine closure plans are based do not consider sample mineralogy or the kinetics of the acid-generating and-neutralizing reactions. Erroneous test interpretations and predictions can result. The importance of considering mineralogy for site-specific interpretation is highlighted. Uncertainty in prediction leads to difficulties for the mine operator in developing satisfactory and cost-effective control and remediation measures. Thus, the application of regulations and guidelines for waste management planning need to beflexible.

Compliant Nanospring Interfaces

DTIC Science & Technology

2017-01-26

for new generation lithium ion batteries ”, Nano Letters, 2015. [21] Krishnan R, Lu TM and Koratkar N, “Functionally strain-graded nanoscoops for high...for Lithium - Ion Batteries , Electrochem. Solid-State Lett. 2003, 6(9), A198-A201. [48] Teki R, Datta MK, Krishnan R, Parker TC, Lu TM, Kumta PN and...Koratkar N. Nanostructured silicon anodes for lithium ion rechargeable batteries , Small, 2009, 5, 2236-2242. [49] Fleischauer MD, Li J and Brett

Abrupt response of chemical weathering to Late Quaternary hydroclimate changes in northeast Africa

PubMed Central

Bastian, Luc; Revel, Marie; Bayon, Germain; Dufour, Aurélie; Vigier, Nathalie

2017-01-01

Chemical weathering of silicate rocks on continents acts as a major sink for atmospheric carbon dioxide and has played an important role in the evolution of the Earth’s climate. However, the magnitude and the nature of the links between weathering and climate are still under debate. In particular, the timescale over which chemical weathering may respond to climate change is yet to be constrained at the continental scale. Here we reconstruct the relationships between rainfall and chemical weathering in northeast Africa for the last 32,000 years. Using lithium isotopes and other geochemical proxies in the clay-size fraction of a marine sediment core from the Eastern Mediterranean Sea, we show that chemical weathering in the Nile Basin fluctuated in parallel with the monsoon-related climatic evolution of northeast Africa. We also evidence strongly reduced mineral alteration during centennial-scale regional drought episodes. Our findings indicate that silicate weathering may respond as quickly as physical erosion to abrupt hydroclimate reorganization on continents. Consequently, we anticipate that the forthcoming hydrological disturbances predicted for northeast Africa may have a major impact on chemical weathering patterns and soil resources in this region. PMID:28290474

Abrupt response of chemical weathering to Late Quaternary hydroclimate changes in northeast Africa.

PubMed

Bastian, Luc; Revel, Marie; Bayon, Germain; Dufour, Aurélie; Vigier, Nathalie

2017-03-14

Chemical weathering of silicate rocks on continents acts as a major sink for atmospheric carbon dioxide and has played an important role in the evolution of the Earth's climate. However, the magnitude and the nature of the links between weathering and climate are still under debate. In particular, the timescale over which chemical weathering may respond to climate change is yet to be constrained at the continental scale. Here we reconstruct the relationships between rainfall and chemical weathering in northeast Africa for the last 32,000 years. Using lithium isotopes and other geochemical proxies in the clay-size fraction of a marine sediment core from the Eastern Mediterranean Sea, we show that chemical weathering in the Nile Basin fluctuated in parallel with the monsoon-related climatic evolution of northeast Africa. We also evidence strongly reduced mineral alteration during centennial-scale regional drought episodes. Our findings indicate that silicate weathering may respond as quickly as physical erosion to abrupt hydroclimate reorganization on continents. Consequently, we anticipate that the forthcoming hydrological disturbances predicted for northeast Africa may have a major impact on chemical weathering patterns and soil resources in this region.

Tuning characteristics of narrowband THz radiation generated via optical rectification in periodically poled lithium niobate.

PubMed

Weiss, C; Torosyan, G; Meyn, J P; Wallenstein, R; Beigang, R; Avetisyan, Y

2001-04-23

The tuning properties of pulsed narrowband THz radiation generated via optical rectification in periodically poled lithium niobate have been investigated. Using a disk-shaped periodically poled crystal tuning was easily accomplished by rotating the crystal around its axis and observing the generated THz radiation in forward direction. In this way no beam deflection during tuning was observed. The total tuning range extended from 180 GHz up to 830 GHz and was limited by the poling period of 127 microm which determines the maximum THz frequency in forward direction.

Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium-Powder Anode for Lithium-Metal Batteries.

PubMed

Shim, Jimin; Lee, Jae Won; Bae, Ki Yoon; Kim, Hee Joong; Yoon, Woo Young; Lee, Jong-Chan

2017-05-22

Lithium-metal anode has fundamental problems concerning formation and growth of lithium dendrites, which prevents practical applications of next generation of high-capacity lithium-metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium-powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium-foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and the structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode material. The effect of the physical state of electrolyte (solid/liquid) and morphology of lithium-metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium-powder anode suggests an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational SN 2-Type Mechanism for the Difluoromethylation of Lithium Enolate with Fluoroform through Bimetallic C-F Bond Dual Activation.

PubMed

Honda, Kazuya; Harris, Travis V; Hatanaka, Miho; Morokuma, Keiji; Mikami, Koichi

2016-06-20

The reaction mechanism for difluoromethylation of lithium enolates with fluoroform was analyzed computationally (DFT calculations with the artificial force induced reaction (AFIR) method and solvation model based on density (SMD) solvation model (THF)), showing an SN 2-type carbon-carbon bond formation; the "bimetallic" lithium enolate and lithium trifluoromethyl carbenoid exert the C-F bond "dual" activation, in contrast to the monometallic butterfly-shaped carbenoid in the Simmons-Smith reaction. Lithium enolates, generated by the reaction of 2 equiv. of lithium hexamethyldisilazide (rather than 1 or 3 equiv.) with the cheap difluoromethylating species fluoroform, are the most useful alkali metal intermediates for the synthesis of pharmaceutically important α-difluoromethylated carbonyl products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiwatt-level continuous-wave midwave infrared generation using difference frequency mixing in periodically poled MgO-doped lithium niobate.

PubMed

Guha, Shekhar; Barnes, Jacob O; Gonzalez, Leonel P

2014-09-01

Over 3.5 W of continuous-wave power at 3.4 μm was obtained by single-pass difference frequency mixing of 1.064 and 1.55 μm fiber lasers in a 5 cm long periodically poled lithium niobate crystal. Good agreement was obtained between the observed temperature dependence of the generated power and the prediction from focused Gaussian beam theory.

Petalite under pressure: Elastic behavior and phase stability

DOE PAGES

Ross, Nancy L.; Zhao, Jing; Slebodnick, Carla; ...

2015-04-01

The lithium aluminosilicate mineral petalite (LiAlSi 4O 10) has been studied using high-pressure single-crystal X-ray diffraction (HP-XRD) up to 5 GPa. Petalite undergoes two pressure-induced first-order phase transitions, never reported in the literature, at ca. 1.5 and 2.5 GPa. The first of these transforms the low-pressure α-phase of petalite (P2/c) to an intermediate β-phase that then fully converts to the high-pressure β-phase at ca. 2.5 GPa. The α→β transition is isomorphic and is associated with a commensurate modulation that triples the unit cell volume. Analysis of the HP-XRD data show that although the fundamental features of the petalite structure aremore » retained through this transition, there are subtle alterations in the internal structure of the silicate double-layers in the β-phase relative to the α-phase. Measurement of the unit cell parameters of petalite as a function of pressure, and fitting of the data with 3rd order Birch-Murnaghan equations of state, has provided revised elastic constants for petalite. The bulk moduli of the α and β-phases are 49(1) and 35(3) GPa, respectively. These values indicate that the compressibility of the- phase of petalite lies between the alkali feldpsars and alkali feldspathoids, whereas the β-phase has a compressibility more comparable with layered silicates. Structure analysis has shown that the compression of the -phase is facilitated by the rigid body movement of the Si 2O 7 units from which the silicate double-layers are constructed.« less

Design and Fabrication of Large Diameter Gradient-Index Lenses for Dual-Band Visible to Short-Wave Infrared Imaging Applications

NASA Astrophysics Data System (ADS)

Visconti, Anthony Joseph

The fabrication of gradient-index (GRIN) optical elements is quite challenging, which has traditionally restricted their use in many imaging systems; consequently, commercial-level GRIN components usually exist in one particular market or niche application space. One such fabrication technique, ion exchange, is a well-known process used in the chemical strengthening of glass, the fabrication of waveguide devices, and the production of small diameter GRIN optical relay systems. However, the manufacturing of large diameter ion-exchanged GRIN elements has historically been limited by long diffusion times. For example, the diffusion time for a 20 mm diameter radial GRIN lens in commercially available ion exchange glass for small diameter relays, is on the order of a year. The diffusion time can be dramatically reduced by addressing three key ion exchange process parameters; the composition of the glass, the diffusion temperature, and the composition of the salt bath. Experimental work throughout this thesis aims to (1) scale up the ion exchange diffusion process to 20 mm diameters for a fast-diffusing titania silicate glass family in both (2) sodium ion for lithium ion (Na+ for Li+) and lithium ion for sodium ion (Li+ for Na+) exchange directions, while (3) utilizing manufacturing friendly salt bath compositions. In addition, optical design studies have demonstrated that an important benefit of gradient-index elements in imaging systems is the added degree of freedom introduced with a gradient's optical power. However, these studies have not investigated the potential usefulness of GRIN materials in dual-band visible to short-wave infrared (vis-SWIR) imaging systems. The unique chromatic properties of the titania silicate ion exchange glass become a significant degree of freedom in the design process for these color-limited, broadband imaging applications. A single GRIN element can replace a cemented doublet or even a cemented triplet, without loss in overall system performance. In this work, a polychromatic vis-SWIR gradient-index design model is constructed based on the homogeneous material properties of the titania silicate ion exchange glass. This model is verified by measuring the dispersion of fabricated GRIN profiles across the vis-SWIR spectrum. Finally, the polychromatic GRIN design model is implemented into commercial design software and several design studies are presented which validate the beneficial chromatic properties of the titania silicate GRIN material. In addition, system-level tolerancing with gradient-index elements is a largely unexplored area. This work introduces new methods and techniques for incorporating GRIN manufacturing errors directly into the design and tolerancing analysis of a multi-element optical system. These methods allow for the optical engineer to utilize manufacturable GRIN profiles throughout the design process and to better predict the final performance of an as-built system. Based on these techniques, a true design-for-manufacture high-performance eyepiece, utilizing a spherical gradient-index element, is designed, toleranced, and commissioned for build.

Electrodics: mesoscale physicochemical interactions in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Mukherjee, Partha P.; Chen, Chien-Fan

2014-06-01

Recent years have witnessed an explosion of interest and research endeavor in lithium-ion batteries to enable vehicle electrification. In particular, a critical imperative is to accelerate innovation for improved performance, life and safety of lithium-ion batteries for electric drive vehicles. Lithium ion batteries are complex, dynamical systems which include a multitude of coupled physicochemical processes encompassing electronic/ionic/diffusive transport in solid/electrolyte phases, electrochemical and phase change reactions and diffusion induced stress generation in multi-scale porous electrode microstructures. While innovations in nanomaterials and nanostructures have spurred the recent advancements, fundamental understanding of the electrode processing - microstructure - performance interplay is of paramount importance. In this presentation, mesoscale physicochemical interactions in lithium-ion battery electrodes will be elucidated.

CAD-FEA modeling and analysis of different full crown monolithic restorations.

PubMed

Dal Piva, Amanda Maria de Oliveira; Tribst, João Paulo Mendes; Borges, Alexandre Luiz Souto; Souza, Rodrigo Othávio de Assunção E; Bottino, Marco Antonio

2018-06-19

To investigate the influence of different materials for monolithic full posterior crowns using 3D-Finite Element Analysis (FEA). Twelve (12) 3D models of adhesively-restored teeth with different crowns according to the material and its elastic modulus were analysed: Acrylic resin, Polyetheretherketone, Composite resin, Hybrid ceramic, pressable and machinable Zirconia reinforced lithium silicate, Feldspathic, Lithium disilicate, Gold alloy, Cobalt-Chromium alloy (Co-Cr), Zirconia tetragonal partially stabilized with yttria, and Alumina. All materials were assumed to behave elastically throughout the entire deformation. Results in restoration and cementing line were obtained using maximum principal stress. In addition, maximum shear stress criteria was used for the cementing line. Restorative materials with higher elastic modulus present higher stress concentration inside the crown, mainly tensile stress on an intaglio surface. On the other hand, materials with lower elastic modulus allow stress passage for cement, increasing shear stress on this layer. Stiffer materials promote higher stress peak values. Materials with higher elastic modulus such as Co-Cr, zirconia and alumina enable higher tensile stress concentration on the crown intaglio surface and higher shear stress on the cement layer, facilitating crown debonding. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

Method of processing "BPS" glass ceramic and seals made therewith

DOEpatents

Reed, Scott T.; Stone, Ronald G.; McCollister, Howard L.; Wengert, deceased, Paul R.

1998-01-01

A glass ceramic composition, a glass ceramic-to-metal seal, and more specifically a hermetic glass ceramic-to-metal seal prepared by subjecting a glass composition comprising, by weight percent, SiO.sub.2 (65-80%), LiO.sub.2 (8-16%), Al.sub.2 O.sub.3 (2-8%), K.sub.2 O (1-8%), P.sub.2 O.sub.5 (1-5%), B.sub.2 O.sub.3 (0.5-7%), and ZnO (0-5%) to the following processing steps: 1) heating the glass composition in a belt furnace to a temperature sufficient to melt the glass and crystallize lithium phosphate, 2) holding at a temperature and for a time sufficient to create cristobalite nuclei, 3) cooling at a controlled rate and to a temperature to cause crystallization of lithium silicates and growth of cristobalite, and 4) still further cooling in stages to ambient temperature. This process produces a glass ceramic whose high coefficient of thermal expansion (up to 200.times.10.sup.-7 in/in/.degree.C.) permits the fabrication of glass ceramic-to-metal seals, and particularly hermetic glass ceramic seals to nickel-based and stainless steel alloys and copper.

Method of processing ``BPS`` glass ceramic and seals made therewith

DOEpatents

Reed, S.T.; Stone, R.G.; McCollister, H.L.; Wengert, P.R.

1998-10-13

A glass ceramic composition, a glass ceramic-to-metal seal, and more specifically a hermetic glass ceramic-to-metal seal prepared by subjecting a glass composition comprising, by weight percent, SiO{sub 2} (65--80%), LiO{sub 2} (8--16%), Al{sub 2}O{sub 3} (2--8%), K{sub 2}O (1--8%), P{sub 2}O{sub 5} (1--5%), B{sub 2}O{sub 3} (0.5--7%), and ZnO (0--5%) to the following processing steps: (1) heating the glass composition in a belt furnace to a temperature sufficient to melt the glass and crystallize lithium phosphate, (2) holding at a temperature and for a time sufficient to create cristobalite nuclei, (3) cooling at a controlled rate and to a temperature to cause crystallization of lithium silicates and growth of cristobalite, and (4) still further cooling in stages to ambient temperature. This process produces a glass ceramic whose high coefficient of thermal expansion (up to 200{times}10{sup {minus}7} in/in/C) permits the fabrication of glass ceramic-to-metal seals, and particularly hermetic glass ceramic seals to nickel-based and stainless steel alloys and copper. 5 figs.

Monte Carlo simulation of the mixed alkali effect with cooperative jumps

NASA Astrophysics Data System (ADS)

Habasaki, Junko; Hiwatari, Yasuaki

2000-12-01

In our previous works on molecular dynamics (MD) simulations of lithium metasilicate (Li2SiO3), it has been shown that the long time behavior of the lithium ions in Li2SiO3 has been characterized by the component showing the enhanced diffusion (Lévy flight) due to cooperative jumps. It has also been confirmed that the contribution of such component decreases by interception of the paths in the mixed alkali silicate (LiKSiO3). Namely, cooperative jumps of like ions are much decreased in number owing to the interception of the path for unlike alkali-metal ions. In the present work, we have performed a Monte Carlo simulation using a cubic lattice in order to establish the role of the cooperative jumps in the transport properties in a mixed alkali glass. Fixed particles (blockage) were introduced instead of the interception of the jump paths for unlike alkali-metal ions. Two types of cooperative motions (a pull type and a push type) were taken into account. Low-dimensionality of the jump path caused by blockage resulted in a decrease of a diffusion coefficient of the particles. The effect of blockage is enhanced when the cooperative motions were introduced.

Impact-generated carbonate melts: evidence from the Haughton structure, Canada

NASA Astrophysics Data System (ADS)

Osinski, Gordon R.; Spray, John G.

2001-12-01

Evidence is presented for the melting of dolomite-rich target rocks during formation of the 24 km diameter, 23 Ma Haughton impact structure on Devon Island in the Canadian high Arctic. Field studies and analytical scanning electron microscopy reveal that the >200 m thick crater-fill deposit, which currently covers an ˜60 km2 area in the center of the structure, comprises fragmented target rocks set within a carbonate-silicate matrix. The silicate component of the matrix consists of Si-Al-Mg-rich glass. The carbonate component is microcrystalline calcite, containing up to a few wt% Si and Al. The calcite also forms spherules and globules within the silicate glass, with which it develops microtextures indicative of liquid immiscibility. Dolomite clasts exhibit evidence of assimilation and may show calcite and rare dolomite overgrowths. Some clasts are penetrated by calcite and silicate injections. Along with the carbonate-silicate glass textures, the presence of pigeonite and spinifex-textured diopside suggests that the matrix to the crater-fill deposit was originally molten and was rapidly cooled. This indicates that the impact event that generated Haughton caused fusion of the predominantly dolomitic target rocks. It appears that the Ca-Mg component of the dolomite may have dissociated, with Mg entering the silicate melt phase, while the Ca component formed a CaCO3-dominant melt. The silicates were derived by the fusion of Lower Paleozoic sandstones, siltstones, shales and impure dolomites. Evidence for melting is corroborated by a review of theoretical and experimental work, which shows that CaCO3 melts at >10 GPa and >2000 K, instead of dissociating to release CO2. This work indicates that carbonate-rich sedimentary targets may also undergo impact melting and that the volume of CO2 released into the atmosphere during such events may be considerably less than previously estimated.

Precipitation of free fatty acids generated by Malassezia - a possible explanation for the positive effects of lithium succinate in seborrhoeic dermatitis.

PubMed

Mayser, P; Schulz, S

2016-08-01

Lithium succinate and gluconate are effective alternative options licensed for the topical treatment of seborrhoeic dermatitis (SD). Their mode of action is not fully elucidated. Minimal inhibitory concentrations against Malassezia (M.) yeasts, which play an important role in SD, are very high. An assay based on the hydrolysis of ethyl octanoate enables us to test the hydrolytic activity of reference strains of the species M. globosa, M. sympodialis and M. furfur solely without interference by fungal growth as the free octanoic acid generated has antifungal activity. In this assay the presence of alkali salts (lithium, sodium and potassium succinate resp.) in concentrations of 2%, 4% and 8% does not influence hydrolytic activity but the availability of the generated free fatty acid in a dose-dependent manner which was analysed by means of high-performance thin layer chromatography and densitometry. This was best effected with the lithium, followed by the sodium and only to a low degree by the potassium salt. As shown by attenuated total reflection Fourier transform infrared spectroscopy the free fatty acid reacted to the respective alkali soap and precipitate from solution. The alkali soaps could not be utilized by the M. spp. as shown in a modified Tween auxanogram and in lack of fungal growth by ethyl oleate in the presence of 8% lithium succinate. The effect of lithium succinate on growth of M. yeasts and presumably in SD can be explained by a precipitation of free fatty acids as alkali soaps limiting their availability for the growth of these lipid-dependent yeasts. © 2016 European Academy of Dermatology and Venereology.

Wear Behavior of Ceramic CAD/CAM Crowns and Natural Antagonists

PubMed Central

Naumova, Ella A.; Schneider, Stephan; Arnold, Wolfgang H.; Piwowarczyk, Andree

2017-01-01

Objective: Evaluation of wear behavior of computer-aided design/computer-aided manufacturing (CAD/CAM) crowns from various restorative materials and natural antagonists. Method: Full CAD/CAM crowns fabricated with nanoceramic resin (Lava Ultimate (LU)), a glass ceramic in a resin interpenetrating matrix (Vita Enamic (VE)) and a lithium silicate reinforced ceramic enriched with zirconia (Vita Suprinity (VS)) were cemented on human molars. The crown and antagonists were subjected to simulated chewing. 3D data sets, before and after the chewing simulation, were generated and matched. Occlusal surface roughness, vertical and volume loss of the crowns and antagonists were analyzed. Results: Crown roughness was significantly different between the LU and VE groups after chewing simulation. Crown vertical loss differed in all groups. The highest crown volume loss was found in the LU group, and the lowest in the VE group. Comparisons between the LU and VE groups and the LU and VS groups were significantly different. The highest antagonist volume loss was reached in the VE group, the lowest was in the LU group. Conclusion: Roughness increased after chewing simulation. LU crowns are the most natural antagonist-friendly; these were the most susceptible to vertical and volume loss. Of the tested materials, the VE crowns are the most stable regarding occlusion. PMID:28772602

Wastewater reuse in liquid sodium silicate manufacturing in alexandria, egypt.

PubMed

Ismail, Gaber A; Abd El-Salam, Magda M; Arafa, Anwar K

2009-01-01

Soluble sodium silicates (waterglass) are liquids containing dissolved glass which have some water like properties. They are widely used in industry as sealants, binders, deflocculants, emulsifiers and buffers. Their most common applications in Egypt are in the pulp and paper industry (where they improve the brightness and efficiency of peroxide bleaching) and the detergent industry, in which they improve the action of the detergent and lower the viscosity of liquid soaps. The survey results showed that the production was carried out batch-wise, in an autoclave (dissolver). Sodium silicate in the state of crushed glass was charged in an autoclave (dissolver) with sodium hydroxide and water. The product is filtered through a press. The left over sludge (mud and silicates impurities) is emptied into the local sewer system. Also, sludge (silica gel) was discharged from the neutralization process of the generated alkaline wastewater and consequently clogging the sewerage system. So this study was carried out to modify the current wastewater management system which eliminates sludge formation, the discharge of higher pH wastewater to the sewer system, and to assess its environmental and economic benefits. To assess the characteristics of wastewater to be reused, physico-chemical parameters of 12 samples were tested using standard methods. The survey results showed that a total capacity of the selected enterprise was 540 tons of liquid sodium silicates monthly. The total amount of wastewater being discharged was 335 m3/month. Reusing of wastewater as feed autoclave water reduced water consumption of 32.1% and reduced wastewater discharge/month that constitutes 89.6% as well as saving in final product of 6 ton/month. It was concluded that reusing of wastewater generated from liquid sodium silicate manufacturing process resulted in cheaper and environmental-friendly product.

First-principles Study on the Charge Transport Mechanism of Lithium Sulfide (Li2 S) in Lithium-Sulfur Batteries.

PubMed

Kim, B S Do-Hoon; Lee, M S Byungju; Park, Kyu-Young; Kang, Kisuk

2016-04-20

The lithium-sulfur chemistry is regarded as a promising candidate for next-generation battery systems because of its high specific energy (1675 mA h g(-1) ). Although issues such as low cycle stability and power capability of the system remain to be addressed, extensive research has been performed experimentally to resolve these problems. Attaining a fundamental understanding of the reaction mechanism and its reaction product would further spur the development of lithium-sulfur batteries. Here, we investigated the charge transport mechanism of lithium sulfide (Li2 S), a discharge product of conventional lithium-sulfur batteries using first-principles calculations. Our calculations indicate that the major charge transport is governed by the lithium-ion vacancies among various possible charge carriers. Furthermore, the large bandgap and low concentration of electron polarons indicate that the electronic conduction negligibly contributes to the charge transport mechanism in Li2 S. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Guoxing; Gao, Yue; He, Xin

Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g -1) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as “plasticizer” in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% overmore » 400 cycles at a current density of 2mAcm -2). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes.« less

Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries

DOE PAGES

Li, Guoxing; Gao, Yue; He, Xin; ...

2017-10-11

Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g -1) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as “plasticizer” in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% overmore » 400 cycles at a current density of 2mAcm -2). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes.« less

Rapid Solidification of a New Generation Aluminum-Lithium Alloy via Electrospark Deposition

NASA Astrophysics Data System (ADS)

Heard, David W.; Boselli, Julien; Gauvin, Raynald; Brochu, Mathieu

Electrospark deposition (ESD) is a rapid solidification processing technique capable of depositing a metal onto a conductive substrate. The short pulse duration and high pulse frequency, combined with the small amount of material transferred during each pulse, results in high cooling rates being realized, on the order of 105-106 C/sec. This study investigates the ability to induce solute trapping behavior, for a new generation aluminum-lithium alloy, AA2199, using ESD.

Synthesis of MoS2 and MoO2 for their applications in H2 generation and lithium ion batteries: a review.

PubMed

Zhao, Yufei; Zhang, Yuxia; Yang, Zhiyu; Yan, Yiming; Sun, Kening

2013-08-01

Scientists increasingly witness the applications of MoS 2 and MoO 2 in the field of energy conversion and energy storage. On the one hand, MoS 2 and MoO 2 have been widely utilized as promising catalysts for electrocatalytic or photocatalytic hydrogen evolution in aqueous solution. On the other hand, MoS 2 and MoO 2 have also been verified as efficient electrode material for lithium ion batteries. In this review, the synthesis, structure and properties of MoS 2 and MoO 2 are briefly summarized according to their applications for H 2 generation and lithium ion batteries. Firstly, we overview the recent advancements in the morphology control of MoS 2 and MoO 2 and their applications as electrocatalysts for hydrogen evolution reactions. Secondly, we focus on the photo-induced water splitting for H 2 generation, in which MoS 2 acts as an important co-catalyst when combined with other semiconductor catalysts. The newly reported research results of the significant functions of MoS 2 nanocomposites in photo-induced water splitting are presented. Thirdly, we introduce the advantages of MoS 2 and MoO 2 for their enhanced cyclic performance and high capacity as electrode materials of lithium ion batteries. Recent key achievements in MoS 2 - and MoO 2 -based lithium ion batteries are highlighted. Finally, we discuss the future scope and the important challenges emerging from these fascinating materials.

Compact high-power red-green-blue laser light source generation from a single lithium tantalate with cascaded domain modulation.

PubMed

Xu, P; Zhao, L N; Lv, X J; Lu, J; Yuan, Y; Zhao, G; Zhu, S N

2009-06-08

1W quasi-white-light source has been generated from a single lithium tantalate with cascaded domain modulation. The quasi-white-light is combined by proper proportion of the red, green and blue laser light. The red and the blue result from a compact self-sum frequency optical parametric oscillation when pumped by a single green laser. The efficiency of quasi-white-light from the green pump reaches 27%. This compact design can be employed not only as a stable and powerful RGB light source but also an effective blue laser generator.

Aperture scaling effects with monolithic periodically poled lithium niobate optical parametric oscillators and generators.

PubMed

Missey, M; Dominic, V; Powers, P; Schepler, K L

2000-02-15

We used elliptical beams to demonstrate aperture scaling effects in nanosecond single-grating and multigrating periodically poled lithium niobate (PPLN) monolithic optical parametric oscillators and generators. Increasing the cavity Fresnel number in single-grating crystals broadened both the beam divergence and the spectral bandwidth. Both effects are explained in terms of the phase-matching geometry. These effects are suppressed when a multigrating PPLN crystal is used because the individual gratings provide small effective subapertures. A flood-pumped multigrating optical parametric generator displayed a low output beam divergence and contained 19 pairs of signal and idler frequencies.

In Situ Analysis of Gas Generation in Lithium-Ion Batteries with Different Carbonate-Based Electrolytes.

PubMed

Teng, Xin; Zhan, Chun; Bai, Ying; Ma, Lu; Liu, Qi; Wu, Chuan; Wu, Feng; Yang, Yusheng; Lu, Jun; Amine, Khalil

2015-10-21

Gas generation in lithium-ion batteries is one of the critical issues limiting their safety performance and lifetime. In this work, a set of 900 mAh pouch cells were applied to systematically compare the composition of gases generated from a serial of carbonate-based composite electrolytes, using a self-designed gas analyzing system. Among electrolytes used in this work, the composite γ-butyrolactone/ethyl methyl carbonate (GBL/EMC) exhibited remarkably less gassing because of the electrochemical stability of the GBL, which makes it a promising electrolyte for battery with advanced safety and lifetime.

Method for generating extreme ultraviolet with mather-type plasma accelerators for use in Extreme Ultraviolet Lithography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hassanein, Ahmed; Konkashbaev, Isak

A device and method for generating extremely short-wave ultraviolet electromagnetic wave uses two intersecting plasma beams generated by two plasma accelerators. The intersection of the two plasma beams emits electromagnetic radiation and in particular radiation in the extreme ultraviolet wavelength. In the preferred orientation two axially aligned counter streaming plasmas collide to produce an intense source of electromagnetic radiation at the 13.5 nm wavelength. The Mather type plasma accelerators can utilize tin, or lithium covered electrodes. Tin, lithium or xenon can be used as the photon emitting gas source.

Three-Dimensional Digital Evaluation of the Fit of Endocrowns Fabricated from Different CAD/CAM Materials.

PubMed

Zimmermann, Moritz; Valcanaia, Andre; Neiva, Gisele; Mehl, Albert; Fasbinder, Dennis

2018-03-06

A wide variety of CAD/CAM materials are available for single-tooth restorations. CAD/CAM material characteristics are different and may influence CAM fabrication accuracy. There is no study investigating the influence of different CAD/CAM materials on the final fit of the restoration. The aim of this study was to evaluate the fit of endocrowns fabricated from different CAD/CAM materials using a new 3D evaluation method with an intraoral scanning system. The null hypothesis was that there are no significant differences for the fitting accuracy of different CAD/CAM materials. Preparation for an endocrown was performed on a maxillary right first molar on a typodont, and restorations were fabricated with a chairside CAD/CAM system (CEREC Omnicam, MCXL). Three groups using three different CAD/CAM materials were established (each n = 10): zirconia-reinforced lithium silicate ceramic (Celtra Duo; CD), leucite-reinforced silicate ceramic (Empress CAD; EM), resin nanoceramic (Lava Ultimate; LU). A 3D digital measurement technique (OraCheck, Cyfex AG) using an intraoral scanner (CEREC Omnicam) was used to measure the difference in fit between the three materials for a master endocrown preparation. The preparation scan and the endocrown fit scan were matched with special difference analysis software OraCheck. Three areas were selected for fitting accuracy measurements: margin (MA), axial (AX), occlusal (OC). Statistical analysis was performed using 80% percentile, one-way ANOVA, and post-hoc Scheffé test. Significance level was set to p = 0.05. Results varied from best 88.9 ± 7.7 μm for marginal fit of resin nanoceramic restorations (LU_MA) to worst 182.3 ± 24.0 μm for occlusal fit of zirconia-reinforced lithium silicate restorations (CD_OC). Statistically significant differences were found both within and among the test groups. Group CD performed statistically significantly different from group LU for marginal fit (MA) and axial fit (AX) (p < 0.05). For occlusal fit (OC), no statistically significant differences were found within all three test groups (p > 0.05). Deviation pattern for differences was visually analyzed with a color-coded scheme for each restoration. Statistically significant differences were found for different CAD/CAM materials if the CAM procedure was identical. Within the limitations of this study, the choice of CAD/CAM material may influence the fitting accuracy of CAD/CAM-fabricated restorations. © 2018 by the American College of Prosthodontists.

Nucleation and Crystallization as Induced by Bending Stress in Lithium Silicate Glass Fibers

NASA Technical Reports Server (NTRS)

Reis, Signo T.; Kim, Cheol W.; Brow, Richard K.; Ray, Chandra S.

2003-01-01

Glass Fibers of Li2O.2SiO2 (LS2) and Li2O.1.6SiO2 (LS1.6) compositions were heated near, but below, the glass transition temperature for different times while subjected to a constant bending stress of about 1.2 GPa. The nucleation density and the crystallization tendency estimated by differential thermal analysis (DTA) of a glass sample in the vicinity of the maximum of the bending stress increased relative to that of stress-free glass fibers. LS2 glass fibers were found more resistant to nucleation and crystallization than the Ls1.6 glass fibers. These results are discussed in regards to shear thinning effects on glass stability.

Methods of repairing a substrate

NASA Technical Reports Server (NTRS)

Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

2011-01-01

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium boride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Multiple generations of grain aggregation in different environments preceded solar system body formation.

PubMed

Ishii, Hope A; Bradley, John P; Bechtel, Hans A; Brownlee, Donald E; Bustillo, Karen C; Ciston, James; Cuzzi, Jeffrey N; Floss, Christine; Joswiak, David J

2018-06-26

The solar system formed from interstellar dust and gas in a molecular cloud. Astronomical observations show that typical interstellar dust consists of amorphous ( a -) silicate and organic carbon. Bona fide physical samples for laboratory studies would yield unprecedented insight about solar system formation, but they were largely destroyed. The most likely repositories of surviving presolar dust are the least altered extraterrestrial materials, interplanetary dust particles (IDPs) with probable cometary origins. Cometary IDPs contain abundant submicron a- silicate grains called GEMS (glass with embedded metal and sulfides), believed to be carbon-free. Some have detectable isotopically anomalous a- silicate components from other stars, proving they are preserved dust inherited from the interstellar medium. However, it is debated whether the majority of GEMS predate the solar system or formed in the solar nebula by condensation of high-temperature (>1,300 K) gas. Here, we map IDP compositions with single nanometer-scale resolution and find that GEMS contain organic carbon. Mapping reveals two generations of grain aggregation, the key process in growth from dust grains to planetesimals, mediated by carbon. GEMS grains, some with a- silicate subgrains mantled by organic carbon, comprise the earliest generation of aggregates. These aggregates (and other grains) are encapsulated in lower-density organic carbon matrix, indicating a second generation of aggregation. Since this organic carbon thermally decomposes above ∼450 K, GEMS cannot have accreted in the hot solar nebula, and formed, instead, in the cold presolar molecular cloud and/or outer protoplanetary disk. We suggest that GEMS are consistent with surviving interstellar dust, condensed in situ, and cycled through multiple molecular clouds. Copyright © 2018 the Author(s). Published by PNAS.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Younesi, Reza; Veith, Gabriel M.; Johansson, Patrik

Presently lithium hexafluorophosphate (LiPF 6) is the dominant Li-salt used in commercial rechargeable lithium-ion batteries (LIBs) based on a graphite anode and a 3-4 V cathode material. While LiPF 6 is not the ideal Li-salt for every important electrolyte property, it has a uniquely suitable combination of properties (temperature range, passivation, conductivity, etc.) rendering it the overall best Li-salt for LIBs. However, this may not necessarily be true for other types of Li-based batteries. Indeed, next generation batteries, for example lithium-metal (Li-metal), lithium-oxygen (Li-O 2), and lithium sulphur (Li-S), require a re-evaluation of Li-salts due to the different electrochemical andmore » chemical reactions and conditions within such cells. Furthermore, this review explores the critical role Li-salts play in ensuring in these batteries viability.« less

Fe{sub 2}O{sub 3}-Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses as lithium-free nonsilicate pH responsive glasses – Compatibility between pH responsivity and hydrophobicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hashimoto, Tadanori, E-mail: hasimoto@chem.mie-u.ac.jp; Hamajima, Mitsuaki; Ohta, Honami

Highlights: • Fe{sub 2}O{sub 3}-rich FeBiB glasses show high pH sensitivity and short pH response time. • Bi{sub 2}O{sub 3}-rich FeBiB glasses show relatively high contact angle for water. • FeBiB glasses are lithium-free nonsilicate pH responsive ones. • pH responsivity and hydrophobicity are obtained for optimum glass compositions. - Abstract: Lithium silicate-based glasses have widely been used as commercially available pH glass electrodes. It was revealed that Ti{sup 3+}-containing titanophosphate (TiO{sub 2}-P{sub 2}O{sub 5}, TP) glasses are pH responsive as lithium-free nonsilicate glasses for the first time. TP glasses with the compatibility between pH responsivity and self-cleaning property weremore » obtained by the sequential post-annealing (oxidation and reduction) of as-prepared glasses. Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} (BiB) glasses are relatively hydrophobic and are expected to show anti-fouling effect. They are unsuitable for pH responsive glasses, because they have high electrical resistivity. In the present study, xFe{sub 2}O{sub 3}·yBi{sub 2}O{sub 3}·(100 − x − y)B{sub 2}O{sub 3} glasses (xFeyBiB, x = 0–20 mol%, y = 20–80 mol%) glasses were selected as new pH responsive glasses with hydrophobicity, because Fe{sub 2}O{sub 3} is a representative component for causing hopping conduction to the glasses. BiB glass did not show pH responsivity, whereas xFeyBiB glasses showed good pH responsivity. xFeyBiB glasses are lithium-free nonsilicate pH responsive ones as well as TP glasses. The electrical resistivity and pH response time decreased with increasing Fe{sub 2}O{sub 3} content. The pH repeatability for standard solutions increased with increasing Bi{sub 2}O{sub 3} content. Silicate glass (20Fe70BiSi) showed better pH responsivity but lower contact angle than those of borate glass (20Fe70BiB). pH sensitivity increased in order of TP glasses (about 80%), xFeyBiB glasses (about 90%) and commercial pH responsive glass (about 100%). xFeyBiB glasses showed short pH response time compared to commercial pH responsive glass. The contact angle for water of xFeyBiB glasses was relatively high (about 90°) as well as BiB glasses, and increased slightly with increasing Bi{sub 2}O{sub 3} content regardless Fe{sub 2}O{sub 3} content. The high contact angle was related to low OH content determined by FT-IR measurement. Thus, 20Fe{sub 2}O{sub 3}·70Bi{sub 2}O{sub 3}·10B{sub 2}O{sub 3} glass was the most suitable one as pH responsive glasses with hydrophobicity. TP glasses are pH responsive ones with self-cleaning property, whereas xFeyBiB glasses are expected as pH responsive ones with anti-fouling property based on hydrophobicity.« less

Calorimetry of 25 Ah lithium/thionyl chloride cells

NASA Technical Reports Server (NTRS)

Johnson, C. J.; Dawson, S.

1991-01-01

Heat flow measurements of 25-Ah lithium thionyl chloride cells provided a method to calculate an effective thermal potential, E(TP) of 3.907 V. The calculation is useful to determine specific heat generation of this cell chemistry and design. The E(TP) value includes heat generation by electrochemical cell reactions, competitive chemical reactions, and resistance heating at the tabs, connectors, and leads. Heat flow was measured while applying electrical loads to the cell in an isothermal calorimeter set at 0, 20, and 60 C.

Preliminary Evaluations of Polymer-based Lithium Battery Electrolytes Under Development for the Polymer Electrolyte Rechargeable Systems Program

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Bennett, William R.

2003-01-01

A component screening facility has been established at The NASA Glenn Research Center (GRC) to evaluate candidate materials for next generation, lithium-based, polymer electrolyte batteries for aerospace applications. Procedures have been implemented to provide standardized measurements of critical electrolyte properties. These include ionic conductivity, electronic resistivity, electrochemical stability window, cation transference number, salt diffusion coefficient and lithium plating efficiency. Preliminary results for poly(ethy1ene oxide)-based polymer electrolyte and commercial liquid electrolyte are presented.

Generation of volcanic ash: a textural study of ash produced in various laboratory experiments

NASA Astrophysics Data System (ADS)

Lavallée, Yan; Kueppers, Ulrich; Dingwell, Donald B.

2010-05-01

In volcanology, ash is commonly understood as a fragment of a bubble wall that gets disrupted during explosive eruptions. Most volcanic ashes are indeed the product of explosive eruptions, but the true definition is however that of a particle size being inferior to 2 mm. The term does not hold any information about its genesis. During fragmentation, particles of all sizes in various amounts are generated. In nature, fragmentation is a brittle response of the material (whether a rock or magma) caused by changes in 1) strain rate and 2) temperature, and/or 3) chemical composition. Here we used different experimental techniques to produce ash and study their physical characteristics. The effects of strain rate were investigated by deforming volcanic rocks and magma (pure silicate melt and crystal-bearing magma) at different temperatures and stresses in a uniaxial compression apparatus. Failure of pure silicate melts is spontaneous and generates more ash particles than fragmentation of crystal-bearing melts. In the latter, the abundance of generated ash correlates positively with the strain rate. We complemented this investigation with a study of particles generated during rapid decompression of porous rocks, using a fragmentation apparatus. Products of decompression experiments at different initial applied pore pressure show that the amount of ash generated by bubble burst increase with the initial applied pressure and the open porosity. The effects of temperature were investigated by dropping pure silicate melts and crystal-bearing magma at 900 and 1100°C in water at room temperature. Quenching of the material is accompanied by rapid contraction and near instantaneous fragmentation. Pure silicate melts respond more violently to the interaction with water and completely fragmented into small particles, including a variety of ash morphologies and surface textures. Crystal-bearing magmas however fragmented only very partially when in contact with water and produced a few ash particles (< 0.05 g). The morphology and surface textures of the experimentally generated ash particles were imaged through scanning electron microscopy, and the observations will be discussed in terms of fragmentation processes.

Ohm's Law, Batteries, and the Clean Energy Landscape

NASA Astrophysics Data System (ADS)

Balsara, Nitash

The need for creating safe electrolytes for lithium batteries is significant given the continued safety problems associated with current lithium-ion batteries. Nonflammable polymer electrolytes offer a possible solution but the rate of lithium ion transport is too low for practical applications. In this talk, I will discuss some of the fundamental factors that limit ion transport in polymers. Polymer electrolytes obey Ohm's Law, i.e. in the limit of small applied potentials, the current generated at steady state is proportional to the applied potential. Factors that determine the current generated will be determined using the continuum theory of Newman. Independent measurements of ion diffusion by pulsed-field gradient NMR will also be presented. The talk will end with a discussion of the possibility of commercializing all-solid batteries with polymer electrolytes.

Effect of Sodium Carboxymethyl Celluloses on Water-catalyzed Self-degradation of 200-degree C-heated Alkali-Activated Cement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sugama T.; Pyatina, T.

2012-05-01

We investigated the usefulness of sodium carboxymethyl celluloses (CMC) in promoting self-degradation of 200°C-heated sodium silicate-activated slag/Class C fly ash cementitious material after contact with water. CMC emitted two major volatile compounds, CO2 and acetic acid, creating a porous structure in cement. CMC also reacted with NaOH from sodium silicate to form three water-insensitive solid reaction products, disodium glycolate salt, sodium glucosidic salt, and sodium bicarbonate. Other water-sensitive solid reaction products, such as sodium polysilicate and sodium carbonate, were derived from hydrolysates of sodium silicate. Dissolution of these products upon contact with water generated heat that promoted cement’s self-degradation. Thus,more » CMC of high molecular weight rendered two important features to the water-catalyzed self-degradation of heated cement: One was the high heat energy generated in exothermic reactions in cement; the other was the introduction of extensive porosity into cement.« less

Spectroscopy `outside the box': Towards wider application of NMR to minerals and glasses with abundant paramagnetic cations - Fe, Ni, Co, and Cu silicates

NASA Astrophysics Data System (ADS)

Stebbins, J. F.

2017-12-01

Since the early applications of solid-state NMR (Nuclear Magnetic Resonance) to silicates in the early 1980's, this powerful method has been widely applied to problems of short- to medium-range structure, particularly for materials in which order/disorder is critical, such as crystalline solid solutions, glasses, and even melts. However, almost all such work has been on materials with low (< a few %) contents of ions with unpaired electron spins. Such spins interact strongly with NMR-observed nuclear spins, and can cause severe line broadening and loss of information, in some cases making spectra nearly unobservable. Many groups of minerals with abundant, paramagnetic transition metals (notably Fe2+) and rare earth cations, as well as wide, petrologically important ranges of glass composition have thus been excluded. Inspired by in-depth NMR studies of 31P, 7Li, and other nuclides in lithium-transition metal oxide and phosphate battery materials (C. Grey and others), and with some serendipitous discovery plus persistence to look far outside of "normal" parameter space, we have recently shown that high resolution, structurally informative spectra can actually be obtained for silicate, oxide, and phosphate solid solutions with moderate (0.1 up to 10%) contents of paramagnetic cations such as Fe2+, Ni2+, Co2+ and REE3+. Very recently we have extended this to observe some of the first quantitative NMR spectra of silicate minerals in which a paramagnetic transition metal is the major cation, obtaining useful data for a series of Cu2+ silicates, fayalite (Fe2SiO4) and Ni- and Co- equivalents of diopside (CaMSi2O6). New data for glasses of the latter compositions may be the first such accurate results for any transition metal-rich glass. Although we are still far from a detailed theoretical understanding of these data, the spectra for the glasses are quite different from those of the crystals, suggesting the possibility of medium-range ordering and clustering of NiO and CoO-rich regions. If this conclusion holds up, it may have major implications for thermodynamic models of activities of such components in melts, which in turn are important for a number of geothermometers and barometers based on mineral-melt partitioning.

Three-dimensional imaging of sulfides in silicate rocks at submicron resolution with multiphoton microscopy.

PubMed

Bénard, Antoine; Palle, Sabine; Doucet, Luc Serge; Ionov, Dmitri A

2011-12-01

We report the first application of multiphoton microscopy (MPM) to generate three-dimensional (3D) images of natural minerals (micron-sized sulfides) in thick (∼120 μm) rock sections. First, reflection mode (RM) using confocal laser scanning microscopy (CLSM), combined with differential interference contrast (DIC), was tested on polished sections. Second, two-photon fluorescence (TPF) and second harmonic signal (SHG) images were generated using a femtosecond-laser on the same rock section without impregnation by a fluorescent dye. CSLM results show that the silicate matrix is revealed with DIC and RM, while sulfides can be imaged in 3D at low resolution by RM. Sulfides yield strong autofluorescence from 392 to 715 nm with TPF, while SHG is only produced by the embedding medium. Simultaneous recording of TPF and SHG images enables efficient discrimination between different components of silicate rocks. Image stacks obtained with MPM enable complete reconstruction of the 3D structure of a rock slice and of sulfide morphology at submicron resolution, which has not been previously reported for 3D imaging of minerals. Our work suggests that MPM is a highly efficient tool for 3D studies of microstructures and morphologies of minerals in silicate rocks, which may find other applications in geosciences.

Andesites from northeastern Kanaga Island, Aleutians

NASA Astrophysics Data System (ADS)

Brophy, James G.

1990-04-01

Kanaga island is located in the central Aleutian island arc. Northeastern Kanaga is a currently active late Tertiary to Recent calc-alkaline volcanic complex. Basaltic andesite to andesite lavas record three episodes (series) of volcanic activity. Series I and Series II lavas are all andesite while Series III lavas are basaltic andesite to andesite. Four Series II andesites contain abundant quenched magmatic inclusions ranging in composition from high-MgO low-alumina basalt to low-MgO highalumina basalt. The spectrum of lava compositions is due primarily to fractional crystallization of a parental low-MgO high-alumina basalt but with variable degrees of crustal contamination and magma mixing. The earliest Series I lavas represent mixing between high-alumina basalt and silicic andesite with maximum SiO2 contents of 65 67 wt %. Later Series I and all Series II lavas are due to mixing of andesite magmas of similar composition. The maximum SiO2 content of the pre-mixed andesites magmas is estimated at 60 63 wt %. The youngest lavas (Series III) are all non-mixed and have maximum estimated SiO2 contents of 59 wt %. The earliest Series I lavas contain a significant crustal component while all later lavas do not. It is concluded that the maximum SiO2 contents of silicic magmas, the contribution of crustal material to silicic magma generation, and the role of magma mixing all decrease with time. Furthermore, silicic magmas generated by fractional crystallization at this volcanic center have a maximum SiO2 content of 63 wt %. All of these features have also been documented at the central Aleutian Cold Bay Volcanic Center (Brophy 1987). Based on data from these two centers a model of Aleutian calc-alkaline magma chamber development is proposed. The main features are: (1) a single low pressure magma chamber is continuously supplied by primitive low-alumina basalt; (2) non-primary high-alumina basalt is formed along the chamber margins by selective gravitational settling of olivine and clinopyroxene and retention of plagioclase; (3) sidewall crystallization accompanied by crustal melting produces buoyant silicic (>63 wt % SiO2) liquids that pond at the top of the chamber, and; (4) continued sidewall crystallization, now isolated from the chamber wall, produces silicic liquids with ≤63 wt % SiO2 that increase the thickness and lowers the overall SiO2 content of the upper silicic zone. It is suggested that the maximum SiO2 content of 63% imposed on fractionation-generated magmas is due to a rheological barrier that prohibits the extraction of more silicic liquids from a crystal-liquid mush along the chamber wall.

Dual-Layered Film Protected Lithium Metal Anode to Enable Dendrite-Free Lithium Deposition.

PubMed

Yan, Chong; Cheng, Xin-Bing; Tian, Yang; Chen, Xiang; Zhang, Xue-Qiang; Li, Wen-Jun; Huang, Jia-Qi; Zhang, Qiang

2018-06-01

Lithium metal batteries (such as lithium-sulfur, lithium-air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next-generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short-circuit and thermal runaway of the rechargeable batteries. Herein, a dual-layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual-layered feature with organic components (ROCO 2 Li and ROLi) on the top and abundant inorganic components (Li 2 CO 3 and LiF) in the bottom. The dual-layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite-free Li metal anode. This work demonstrates the concept of rational construction of dual-layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Novel Optical Diagnostic for In Situ Measurements of Lithium Polysulfides in Battery Electrolytes.

PubMed

Saqib, Najmus; Silva, Cody J; Maupin, C Mark; Porter, Jason M

2017-07-01

An optical diagnostic technique to determine the order and concentration of lithium polysulfides in lithium-sulfur (Li-S) battery electrolytes has been developed. One of the major challenges of lithium-sulfur batteries is the problem of polysulfide shuttling between the electrodes, which leads to self-discharge and loss of active material. Here we present an optical diagnostic for quantitative in situ measurements of lithium polysulfides using attenuated total reflection Fourier transform infrared (FT-IR) spectroscopy. Simulated infrared spectra of lithium polysulfide molecules were generated using computational quantum chemistry routines implemented in Gaussian 09. The theoretical spectra served as a starting point for experimental characterization of lithium polysulfide solutions synthesized by the direct reaction of lithium sulfide and sulfur. Attenuated total reflection FT-IR spectroscopy was used to measure absorption spectra. The lower limit of detection with this technique is 0.05 M. Measured spectra revealed trends with respect to polysulfide order and concentration, consistent with theoretical predictions, which were used to develop a set of equations relating the order and concentration of lithium polysulfides in a sample to the position and area of a characteristic infrared absorption band. The diagnostic routine can measure the order and concentration to within 5% and 0.1 M, respectively.

Impact of lithium alone or in combination with haloperidol on oxidative stress parameters and cell viability in SH-SY5Y cell culture.

PubMed

Gawlik-Kotelnicka, Oliwia; Mielicki, Wojciech; Rabe-Jabłońska, Jolanta; Lazarek, Jerry; Strzelecki, Dominik

2016-02-01

It has been reported that lithium may inhibit lipid peroxidation and protein oxidation. Lithium salts also appear to stimulate cell proliferation, increase neurogenesis, and delay cell death. Oxidative stress and neurodegeneration may play an important role in the pathophysiology of bipolar disorder and the disease course thereof. The aim of this research is to estimate the influence of lithium (alone and in combination with haloperidol) on the parameters of oxidative stress and viability of SH-SY5Y cell lines in neutral and pro-oxidative conditions. The evaluated oxidative stress parameter was lipid peroxidation. The viability of the cell lines was measured utilising the MTT test. In neutral conditions, higher levels of thiobarbituric acid reactive substances were observed in those samples which contained both haloperidol and lithium than in other samples. However, these differences were not statistically significant. Cell viability was significantly higher in therapeutic lithium samples than in the controls; samples of haloperidol alone as well as those of haloperidol with lithium did not differ from controls. The results of our study may indicate that lithium possess neuroprotective properties that may be partly due to antioxidative effects. The combination of lithium and haloperidol may generate increased oxidative stress.

Sustainable governance of scarce metals: the case of lithium.

PubMed

Prior, Timothy; Wäger, Patrick A; Stamp, Anna; Widmer, Rolf; Giurco, Damien

2013-09-01

Minerals and metals are finite resources, and recent evidence suggests that for many, primary production is becoming more difficult and more expensive. Yet these resources are fundamentally important for society--they support many critical services like infrastructure, telecommunications and energy generation. A continued reliance on minerals and metals as service providers in modern society requires dedicated and concerted governance in relation to production, use, reuse and recycling. Lithium provides a good example to explore possible sustainable governance strategies. Lithium is a geochemically scarce metal (being found in a wide range of natural systems, but in low concentrations that are difficult to extract), yet recent studies suggest increasing future demand, particularly to supply the lithium in lithium-ion batteries, which are used in a wide variety of modern personal and commercial technologies. This paper explores interventions for sustainable governance and handling of lithium for two different supply and demand contexts: Australia as a net lithium producer and Switzerland as a net lithium consumer. It focuses particularly on possible nation-specific issues for sustainable governance in these two countries' contexts, and links these to the global lithium supply chain and demand scenarios. The article concludes that innovative business models, like 'servicizing' the lithium value chain, would hold sustainable governance advantages for both producer and consumer countries. Copyright © 2013 Elsevier B.V. All rights reserved.

Nanostructured Metal Oxides and Sulfides for Lithium-Sulfur Batteries.

PubMed

Liu, Xue; Huang, Jia-Qi; Zhang, Qiang; Mai, Liqiang

2017-05-01

Lithium-sulfur (Li-S) batteries with high energy density and long cycle life are considered to be one of the most promising next-generation energy-storage systems beyond routine lithium-ion batteries. Various approaches have been proposed to break down technical barriers in Li-S battery systems. The use of nanostructured metal oxides and sulfides for high sulfur utilization and long life span of Li-S batteries is reviewed here. The relationships between the intrinsic properties of metal oxide/sulfide hosts and electrochemical performances of Li-S batteries are discussed. Nanostructured metal oxides/sulfides hosts used in solid sulfur cathodes, separators/interlayers, lithium-metal-anode protection, and lithium polysulfides batteries are discussed respectively. Prospects for the future developments of Li-S batteries with nanostructured metal oxides/sulfides are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insight into self-discharge of layered lithium-rich oxide cathode in carbonate-based electrolytes with and without additive

NASA Astrophysics Data System (ADS)

Li, Jianhui; Xing, Lidan; Zhang, Liping; Yu, Le; Fan, Weizhen; Xu, Mengqing; Li, Weishan

2016-08-01

Self-discharge behavior of layered lithium-rich oxide as cathode of lithium ion battery in a carbonated-based electrolyte is understood, and a simple boron-containing compound, trimethyl borate (TMB), is used as an electrolyte additive to suppress this self-discharge. It is found that layered lithium-rich oxide charged under 4.8 V in additive-free electrolyte suffers severe self-discharge and TMB is an effective electrolyte additive for self-discharge suppression. Physical characterizations from XRD, SEM, TEM, XPS and ICP-MS demonstrate that the crystal structure of the layered lithium-rich oxide collapses due to the chemical interaction between the charged oxide and electrolyte. When TMB is applied, the structural integrity of the oxide is maintained due to the protective cathode film generated from the preferential oxidation of TMB.

Current limit diagrams for dendrite formation in solid-state electrolytes for Li-ion batteries

NASA Astrophysics Data System (ADS)

Raj, R.; Wolfenstine, J.

2017-03-01

We build upon the concept that nucleation of lithium dendrites at the lithium anode-solid state electrolyte interface is instigated by the higher resistance of grain boundaries that raises the local electro-chemical potential of lithium, near the lithium-electrode. This excess electro-chemo-mechanical potential, however, is reduced by the mechanical back stress generated when the dendrite is formed within the electrolyte. These parameters are coalesced into an analytical model that prescribes a specific criterion for dendrite formation. The results are presented in the form of current limit diagrams that show the "safe" and "fail" regimes for battery function. A higher conductivity of the electrolyte can reduce dendrite formation.

Polymer Energy Rechargeable System Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

2003-01-01

Long description. Illustrations of discotic liquid crystals, rod-coil polymers, lithium-ion conducting channel dilithium phthalocyanine (Li2Pc) from top and side, novel star polyethylene oxide structures, composite polyethylene oxide materials (showing polyethylene oxide + lithium salt, carbon atoms and oxygen atoms), homopolyrotaxanes, and diblock copolymers In fiscal year 2000, NASA established a program to develop the next generation, lithium-based, polymer electrolyte batteries for aerospace applications. The goal of this program, known as Polymer Energy Rechargeable Systems (PERS), is to develop a space-qualified, advanced battery system embodying polymer electrolyte and lithium-based electrode technologies and to establish world-class domestic manufacturing capabilities for advanced batteries with improved performance characteristics that address NASA s future aerospace battery requirements.

Lithium conductivity in an Li-bearing double-ring silicate mineral, sogdianite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, S.-H.; Hoelzel, M.; Forschungsneutronenquelle Heinz Maier-Leibnitz

The crystal structure of an Li-bearing double-ring silicate mineral, sogdianite ((Zr{sub 1.18}Fe{sup 3+} {sub 0.55}Ti{sub 0.24}Al{sub 0.03})(Y {sub 1.64},Na{sub 0.36})K{sub 0.85}[Li{sub 3}Si{sub 12}O{sub 30}], P6/mcc, a{approx}10.06 A, c{approx}14.30 A, Z=2), was investigated by neutron powder diffraction from 300 up to 1273 K. Rietveld refinements of displacement parameters revealed high anisotropic Li motions perpendicular to the crystallographic c-axis, indicating an exchange process between tetrahedral T2 and octahedral A sites. AC impedance spectra of a sogdianite single crystal (0.04x0.09x0.25 cm{sup 3}) show that the material is an ionic conductor with conductivity values of {sigma}=4.1x10{sup -5} S cm{sup -1} at 923 K andmore » 1.2x10{sup -3} S cm{sup -1} at 1219 K perpendicular to the c-axis, involving two relaxation processes with activation energies of 1.26(3) and 1.08(3) eV, respectively. - Graphical abstract: Structure of sogdianite with atomic displacement parameter (ADP) ellipsoids at 1273 K.« less

An efficient method for supercontinuum generation in dispersion-tailored Lead-silicate fiber taper

NASA Astrophysics Data System (ADS)

Chen, Z.; Ma, S.; Dutta, N. K.

2010-08-01

In this paper we theoretically study the broadband mid-IR supercontinuum generation (SCG) in a lead-silicate microstructured fiber (the glass for simulation is SF57). The total dispersion of the fiber can be tailored by changing the core diameter of the fiber so that dispersion profiles with two zero dispersion wavelengths (ZDWs) can be obtained. Numerical simulations of the SCG process in a 4 cm long SF57 fiber/fiber taper seeded by femto-second pulses at telecommunications wavelength of 1.55 µm are presented. The results show that a fiber taper features a continuous shift of the longer zero dispersion wavelength. This extends the generated continuum to a longer wavelength region compared to fibers with fixed ZDWs. The phase-matching condition (PMC) is continuously modified in the fiber taper and the bandwidth of the generated dispersive waves (DWs) is significantly broadened.

Ab-initio Calculation of the XANES of Lithium Phosphates and LiFePO4

NASA Astrophysics Data System (ADS)

Yiu, Y. M.; Yang, Songlan; Wang, Dongniu; Sun, Xueliang; Sham, T. K.

2013-04-01

Lithium iron phosphate has been regarded as a promising cathode material for the next generation lithium ion batteries due to its high specific capacity, superior thermal and cyclic stability [1]. In this study, the XANES (X-ray Absorption Near Edge Structure) spectra of lithium iron phosphate and lithium phosphates of various compositions at the Li K, P L3,2, Fe M3,2 and O K-edges have been simulated self-consistently using ab-initio calculations based on multiple scattering theory (the FEFF9 code) and DFT (Density Functional Theory, the Wien2k code). The lithium phosphates under investigation include LiFePO4, γ-Li3PO4, Li4P2O7 and LiPO3. The calculated spectra are compared to the experimental XANES recorded in total electron yield (TEY) and fluorescence yield (FLY). This work was carried out to assess the XANES of possible phases presented in LiFePO4 based Li ion battery applications [2].

The temperature and ion energy dependence of deuterium retention in lithium films

NASA Astrophysics Data System (ADS)

Buzi, Luxherta; Koel, Bruce E.; Skinner, Charles H.

2016-10-01

Lithium conditioning of plasma facing components in magnetic fusion devices has improved plasma performance and lowered hydrogen recycling. For applications of lithium in future high heat flux and long pulse duration machines it is important to understand and parameterize deuterium retention in lithium. This work presents surface science studies of deuterium retention in lithium films as a function of surface temperature, incident deuterium ion energy and flux. Initial experiments are performed on thin (3-30 ML) lithium films deposited on a single crystal molybdenum substrate to avoid effects due to grain boundaries, intrinsic defects and impurities. A monoenergetic and mass-filtered deuterium ion beam was generated in a differentially pumped Colutron ion gun. Auger electron spectroscopy and X-ray photoelectron spectroscopy were used to identify the elemental composition and temperature programmed desorption was used to measure the deuterium retention under the different conditions. Support was provided through DOE Contract Number DE-AC02-09CH11466.

Directing lateral growth of lithium dendrites in micro-compartmented anode arrays for safe lithium metal batteries.

PubMed

Zou, Peichao; Wang, Yang; Chiang, Sum-Wai; Wang, Xuanyu; Kang, Feiyu; Yang, Cheng

2018-01-31

Uncontrolled growth of lithium dendrites during cycling has remained a challenging issue for lithium metal batteries. Thus far, various approaches have been proposed to delay or suppress dendrite growth, yet little attention has been paid to the solutions that can make batteries keep working when lithium dendrites are already extensively present. Here we develop an industry-adoptable technology to laterally direct the growth of lithium dendrites, where all dendrites are retained inside the compartmented copper current collector in a given limited cycling capacity. This featured electrode layout renders superior cycling stability (e.g., smoothly running for over 150 cycles at 0.5 mA cm -2 ). Numerical simulations indicate that reduced dendritic stress and damage to the separator are achieved when the battery is abusively running over the ceiling capacity to generate protrusions. This study may contribute to a deeper comprehension of metal dendrites and provide a significant step towards ultimate safe batteries.

Tradeoff analysis with lithium cells

NASA Technical Reports Server (NTRS)

Bennett, C.

1978-01-01

Characteristic data, primarily on high rate lithium sulfur dioxide design (basically in the D and DD cell configuration), both before and after much exposure to environmental conditions are discussed. The environmental as opposed to signle cells. Discussion was generated among the Workshop participants and comments and questions are reported. Graphical representations of the test data are presented.

The distribution and composition characteristics of siliceous rocks from Qinzhou Bay-Hangzhou Bay joint belt, South China: constraint on the tectonic evolution of plates in South China.

PubMed

Li, Hongzhong; Zhai, Mingguo; Zhang, Lianchang; Zhou, Yongzhang; Yang, Zhijun; He, Junguo; Liang, Jin; Zhou, Liuyu

2013-01-01

The Qinzhou Bay-Hangzhou Bay joint belt is a significant tectonic zone between the Yangtze and Cathaysian plates, where plentiful hydrothermal siliceous rocks are generated. Here, the authors studied the distribution of the siliceous rocks in the whole tectonic zone, which indicated that the tensional setting was facilitating the development of siliceous rocks of hydrothermal genesis. According to the geochemical characteristics, the Neopalaeozoic siliceous rocks in the north segment of the Qinzhou Bay-Hangzhou Bay joint belt denoted its limited width. In comparison, the Neopalaeozoic Qinzhou Bay-Hangzhou Bay joint belt was diverse for its ocean basin in the different segments and possibly had subduction only in the south segment. The ocean basin of the north and middle segments was limited in its width without subduction and possibly existed as a rift trough that was unable to resist the terrigenous input. In the north segment of the Qinzhou Bay-Hangzhou Bay joint belt, the strata of hydrothermal siliceous rocks in Dongxiang copper-polymetallic ore deposit exhibited alternative cycles with the marine volcanic rocks, volcanic tuff, and metal sulphide. These sedimentary systems were formed in different circumstances, whose alternative cycles indicated the release of internal energy in several cycles gradually from strong to weak.

Making Earth's earliest continental crust - an analogue from voluminous Neogene silicic volcanism in NE-Iceland

NASA Astrophysics Data System (ADS)

Berg, Sylvia E.; Troll, Valentin R.; Burchardt, Steffi; Riishuus, Morten S.; Deegan, Frances M.; Harris, Chris; Whitehouse, Martin J.; Gústafsson, Ludvik E.

2014-05-01

Borgarfjörður Eystri in NE-Iceland represents the second-most voluminous exposure of silicic eruptive rocks in Iceland and is a superb example of bimodal volcanism (Bunsen-Daly gap), which represents a long-standing controversy that touches on the problem of crustal growth in early Earth. The silicic rocks in NE-Iceland approach 25 % of the exposed rock mass in the region (Gústafsson et al., 1989), thus they significantly exceed the usual ≤ 12 % in Iceland as a whole (e.g. Walker, 1966; Jonasson, 2007). The origin, significance, and duration of the voluminous (> 300 km3) and dominantly explosive silicic activity in Borgarfjörður Eystri is not yet constrained (c.f. Gústafsson, 1992), leaving us unclear as to what causes silicic volcanism in otherwise basaltic provinces. Here we report SIMS zircon U-Pb ages and δ18O values from the region, which record the commencement of silicic igneous activity with rhyolite lavas at 13.5 to 12.8 Ma, closely followed by large caldera-forming ignimbrite eruptions from the Breiðavik and Dyrfjöll central volcanoes (12.4 Ma). Silicic activity ended abruptly with dacite lava at 12.1 Ma, defining a ≤ 1 Myr long window of silicic volcanism. Magma δ18O values estimated from zircon range from 3.1 to 5.5 (± 0.3; n = 170) and indicate up to 45 % assimilation of a low-δ18O component (e.g. typically δ18O = 0 ‰, Bindeman et al., 2012). A Neogene rift relocation (Martin et al., 2011) or the birth of an off-rift zone to the east of the mature rift associated with a thermal/chemical pulse in the Iceland plume (Óskarsson & Riishuus, 2013), likely brought mantle-derived magma into contact with fertile hydrothermally-altered basaltic crust. The resulting interaction triggered large-scale crustal melting and generated mixed-origin silicic melts. Such rapid formation of silicic magmas from sustained basaltic volcanism may serve as an analogue for generating continental crust in a subduction-free early Earth (e.g. ≥ 3 Ga, Kamber et al., 2005). REFERENCES: Bindeman, I.N., et al., 2012. Terra Nova 24, 227-232. Gústafsson, L.E., et al., 1989. Jökull, v. 39, 75-89. Gústafsson, L.E., 1992. PhD dissertation, Freie Universität Berlin. Jonasson, K., 2007. Journal of Geodynamics, 43, 101-117. Kamber, B.S., et al., 2005. Earth Planet. Sci. Lett., Vol. 240 (2), 276-290. Martin, E., et al., 2011. Earth Planet. Sc. Lett., 311, 28-38. Óskarsson, B.V., & Riishuus, M.S., 2013. J. Volcanol. Geoth.Res., 267, 92-118. Walker, G.P.L., 1966. Bull. Volcanol., 29 (1), 375-402.

In situ TEM study of the Li-Au reaction in an electrochemical liquid cell.

PubMed

Zeng, Zhiyuan; Liang, Wen-I; Chu, Ying-Hao; Zheng, Haimei

2014-01-01

We study the lithiation of a Au electrode in an electrochemical liquid cell using transmission electron microscopy (TEM). The commercial liquid electrolyte for lithium ion batteries (1 M lithium hexafluorophosphate LiPF6 dissolved in 1 : 1 (v/v) ethylene carbonate (EC) and diethyl carbonate (DEC)) was used. Three distinct types of morphology change during the reaction, including gradual dissolution, explosive reaction and local expansion/shrinkage, are observed. It is expected that significant stress is generated from lattice expansion during lithium-gold alloy formation. There is vigorous bubble formation from electrolyte decomposition, likely due to the catalytic effect of Au, while the bubble generation is less severe with titanium electrodes. There is an increase of current in response to electron beam irradiation, and electron beam effects on the observed electrochemical reaction are discussed.

Tunable ultraviolet radiation by second-harmonic generation in periodically poled lithium tantalate.

PubMed

Meyn, J P; Fejer, M M

1997-08-15

We describe electric-field poling of fine-pitch ferroelectric domain gratings in lithium tantalate and characterization of nonlinear-optical properties by single-pass quasi-phase-matched second-harmonic generation (QPM SHG). With a 7.5-microm-period grating, the observed effective nonlinear coefficient for first-order QPM SHG of 532-nm radiation is 9 pm/V, whereas for a grating with a 2.625-microm period, 2.6 pm/V was observed for second-order QPM SHG of 325-nm radiation. These values are 100% and 55% of the theoretically expected values, respectively. We derive a temperature-dependent Sellmeier equation for lithium tantalate that is valid deeper into the UV than currently available results, based on temperature-tuning experiments at different QPM grating periods combined with refractive-index data in the literature.

Next Generation Lithium-Ion Cell For Satellite Applications

NASA Astrophysics Data System (ADS)

Inoue, Takefumi; Segawa, Masazumi; Yoshida, Hiroaki; Takeda, Koichi

2011-10-01

GS Yuasa Technology has standard line up cells for satellite applications since 1999. The design of these cells is not changed and their production will continue. GS Yuasa is now developing higher performance Next Generation Lithium-ion cells. These cells have an improved positive material, negative material, electrolyte, and separator and have demonstrated excellent capacity retention with very low DC resistance growth during life testing. The new cell has approximately 40% more EOL energy (Wh/kg), and slightly lighter weight while using the same size components as our existing products.

HEAT GENERATION

DOEpatents

Imhoff, D.H.; Harker, W.H.

1963-12-01

Heat is generated by the utilization of high energy neutrons produced as by nuclear reactions between hydrogen isotopes in a blanket zone containing lithium, a neutron moderator, and uranium and/or thorium effective to achieve multtplicatton of the high energy neutron. The rnultiplied and moderated neutrons produced react further with lithium-6 to produce tritium in the blanket. Thermal neutron fissionable materials are also produced and consumed in situ in the blanket zone. The heat produced by the aggregate of the various nuclear reactions is then withdrawn from the blanket zone to be used or otherwise disposed externally. (AEC)

[1,5]-Anion relay via intramolecular proton transfer to generate 3,3-bis(silyl) allyloxy lithium: a useful scaffold for syn-addition to aldehydes and ketones.

PubMed

Lin, Xinglong; Ye, Xincui; Sun, Xianwei; Zhang, Yuebao; Gao, Lu; Song, Zhenlei

2014-02-21

A [1,5]-anion relay has been achieved in 3,3-bis(silyl) benzyl enol ether. Deprotonation at the sterically more accessible benzyl position triggers an intramolecular proton transfer to generate the thermodynamically more stable 3,3-bis(silyl) allyloxy lithium. This endo-oriented allyl anion is stable at -78 °C and undergoes diastereoselective syn-addition at the γ-position with aldehydes and ketones to give monobenzyl-substituted 1,2-diols.

Chemical evidence for differentiation, evaporation and recondensation from silicate clasts in Gujba

NASA Astrophysics Data System (ADS)

Oulton, Jonathan; Humayun, Munir; Fedkin, Alexei; Grossman, Lawrence

2016-03-01

The silicate and metal clasts in CB chondrites have been inferred to form as condensates from an impact-generated vapor plume between a metal-rich body and a silicate body. A detailed study of the condensation of impact-generated vapor plumes showed that the range of CB silicate clast compositions could not be successfully explained without invoking a chemically differentiated target. Here, we report the most comprehensive elemental study yet performed on CB silicates with 32 silicate clasts from nine slices of Gujba analyzed by laser ablation inductively coupled plasma mass spectrometry for 53 elements. Like in other studies of CBs, the silicate clasts are either barred olivine (BO) or cryptocrystalline (CC) in texture. In major elements, the Gujba silicate clasts ranged from chondritic to refractory enriched. Refractory element abundances ranged from 2 to 10 × CI, with notable anomalies in Ba, Ce, Eu, and U abundances. The two most refractory-enriched BO clasts exhibited negative Ce anomalies and were depleted in U relative to Th, characteristic of volatilization residues, while other BO clasts and the CC clasts exhibited positive Ce anomalies with excess U (1-3 × CI), and Ba (1-6 × CI) anomalies indicating re-condensation of ultra-refractory element depleted vapor. The Rare Earth Elements (REE) also exhibit light REE (LREE) enrichment or depletion in several clasts with a range of (La/Sm)CI of 0.9-1.8. This variation in the LREE is essentially impossible to accomplish by processes involving vapor-liquid or vapor-solid exchange of REE, and appears to have been inherited from a differentiated target. The most distinctive evidence for inherited chemical differentiation is observed in highly refractory element (Sc, Zr, Nb, Hf, Ta, Th) systematics. The Gujba clasts exhibit fractionations in Nb/Ta that correlate positively with Zr/Hf and span the range known from lunar and Martian basalts, and exceed the range in Zr/Hf variation known from eucrites. Variations of highly incompatible refractory elements (e.g., Th) against less incompatible elements (e.g., Zr, Sr, Sc) are not chondritic, but exhibit distinctly higher Th abundances requiring a differentiated crust to be admixed with depleted mantle in ratios that are biased to higher crust/mantle ratios than in a chondritic body. The possibility that these variations are due to admixture of refractory inclusion-debris into normal chondritic matter is raised but cannot be definitively tested because existing ;bulk; analyses of CAIs carry artifacts of unrepresentative sampling. The inferences drawn from the compositions of Gujba silicate clasts, here, complement what has been inferred from the compositions of metallic clasts, but provide surprisingly detailed insight into the structure of the target. Evidence that metal and silicate in CB chondrites both formed from impact-generated vapor plumes, taken together with recent work on metallic nodules in E chondrites, and on ordinary chondrites, indicates that chondrule formation occurs by this mechanism quite widely. However, the nature of the impact on the CB body is quite different than the popular conceptions of impact of partially or wholly molten chondritic bodies and the younger (5 Ma) age of CB chondrules is consistent with origin in a disk with more evolved targets and impactors gravitationally perturbed by nascent planets.

Lithium target for accelerator based BNCT neutron source: Influence by the proton irradiation on lithium

NASA Astrophysics Data System (ADS)

Fujii, R.; Imahori, Y.; Nakakmura, M.; Takada, M.; Kamada, S.; Hamano, T.; Hoshi, M.; Sato, H.; Itami, J.; Abe, Y.; Fuse, M.

2012-12-01

The neutron source for Boron Neutron Capture Therapy (BNCT) is in the transition stage from nuclear reactor to accelerator based neutron source. Generation of low energy neutron can be achieved by 7Li (p, n) 7Be reaction using accelerator based neutron source. Development of small-scale and safe neutron source is within reach. The melting point of lithium that is used for the target is low, and durability is questioned for an extended use at a high current proton beam. In order to test its durability, we have irradiated lithium with proton beam at the same level as the actual current density, and found no deterioration after 3 hours of continuous irradiation. As a result, it is suggested that lithium target can withstand proton irradiation at high current, confirming suitability as accelerator based neutron source for BNCT.

Lithium metal protection enabled by in-situ olefin polymerization for high-performance secondary lithium sulfur batteries

NASA Astrophysics Data System (ADS)

An, Yongling; Zhang, Zhen; Fei, Huifang; Xu, Xiaoyan; Xiong, Shenglin; Feng, Jinkui; Ci, Lijie

2017-09-01

Lithium metal is considered to be the optimal choice of next-generation anode materials due to its ultrahigh theoretical capacity and the lowest redox potential. However, the growth of dendritic and mossy lithium for rechargeable Li metal batteries lead to the possible short circuiting and subsequently serious safety issues during charge/discharge cycles. For the further practical applications of Li anode, here we report a facile method for fabricating robust interfacial layer via in-situ olefin polymerization. The resulting polymer layer effectively suppresses the formation of Li dendrites and enables the long-term operation of Li metal batteries. Using Li-S cells as a test system, we also demonstrate an improved capacity retention with the protection of tetramethylethylene-polymer. Our results indicate that this method could be a promising strategy to tackle the intrinsic problems of lithium metal anodes and promote the development of Li metal batteries.

Inexpensive method for producing macroporous silicon particulates (MPSPs) with pyrolyzed polyacrylonitrile for lithium ion batteries

PubMed Central

Thakur, Madhuri; Sinsabaugh, Steven L.; Isaacson, Mark J.; Wong, Michael S.; Biswal, Sibani Lisa

2012-01-01

One of the most exciting areas in lithium ion batteries is engineering structured silicon anodes. These new materials promise to lead the next generation of batteries with significantly higher reversible charge capacity than current technologies. One drawback of these materials is that their production involves costly processing steps, limiting their application in commercial lithium ion batteries. In this report we present an inexpensive method for synthesizing macroporous silicon particulates (MPSPs). After being mixed with polyacrylonitrile (PAN) and pyrolyzed, MPSPs can alloy with lithium, resulting in capacities of 1000 mAhg−1 for over 600+ cycles. These sponge-like MPSPs with pyrolyzed PAN (PPAN) can accommodate the large volume expansion associated with silicon lithiation. This performance combined with low cost processing yields a competitive anode material that will have an immediate and direct application in lithium ion batteries. PMID:23139860

High-Performance Lithium-Air Battery with a Coaxial-Fiber Architecture.

PubMed

Zhang, Ye; Wang, Lie; Guo, Ziyang; Xu, Yifan; Wang, Yonggang; Peng, Huisheng

2016-03-24

The lithium-air battery has been proposed as the next-generation energy-storage device with a much higher energy density compared with the conventional lithium-ion battery. However, lithium-air batteries currently suffer enormous problems including parasitic reactions, low recyclability in air, degradation, and leakage of liquid electrolyte. Besides, they are designed into a rigid bulk structure that cannot meet the flexible requirement in the modern electronics. Herein, for the first time, a new family of fiber-shaped lithium-air batteries with high electrochemical performances and flexibility has been developed. The battery exhibited a discharge capacity of 12,470 mAh g(-1) and could stably work for 100 cycles in air; its electrochemical performances were well maintained under bending and after bending. It was also wearable and formed flexible power textiles for various electronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High temperature compounds for turbine vanes

NASA Technical Reports Server (NTRS)

Rhodes, W. H.; Cannon, R. M., Jr.

1972-01-01

Fabrication and microstructure control studies were conducted on SiC, Si3N4, and composites based on these compounds. Charpy mode impact testing to 2400 F established that beta-spodumene, lithium aluminum silicate, coated Si3N4, Si3N4 derived from alpha-Si3N4 powder, and SiC containing 5-25 v/o chopped C fibers had the most promising strengths. Several other composite systems had excellent microstructures and could prove interesting materials in the future. Stress-rupture testing on Si3N4 established that increasing 2000 F - 100 hour strengths were obtained for increasing grain size to at least 5 micrometers, increasing density and possibly increasing phase purity. These parameters became less important at 2400 F where it is thought a grain boundary phase controls strength.

Dispersion dependence of second-order refractive index and complex third-order optical susceptibility in oxide glasses

NASA Astrophysics Data System (ADS)

Abdel Wahab, F. A.; El-Diasty, Fouad; Abdel-Baki, Manal

2009-10-01

A method correlates Fresnel-based spectrophotometric measurements and Lorentz dispersion theory is presented to study the dispersion of nonlinear optical parameters in particularly oxide glasses in a very wide range of angular frequency. The second-order refractive index and third-order optical susceptibility of Cr-doped glasses are determined from linear refractive index. Furthermore, both real and imaginary components of the complex susceptibility are carried out. The study reveals the importance of determining the dispersion of nonlinear absorption (two-photon absorption coefficient) to find the maximum resonant and nonresonant susceptibilities of investigated glasses. The present method is applied on Cr-doped lithium aluminum silicate (LAS) glasses due to their semiconductor-like behavior and also to their application in laser industry.

Multistage leaching of metals from spent lithium ion battery waste using electrochemically generated acidic lixiviant.

PubMed

Boxall, N J; Adamek, N; Cheng, K Y; Haque, N; Bruckard, W; Kaksonen, A H

2018-04-01

Lithium ion battery (LIB) waste contains significant valuable resources that could be recovered and reused to manufacture new products. This study aimed to develop an alternative process for extracting metals from LIB waste using acidic solutions generated by electrolysis for leaching. Results showed that solutions generated by electrolysis of 0.5 M NaCl at 8 V with graphite or mixed metal oxide (MMO) electrodes were weakly acidic and leach yields obtained under single stage (batch) leaching were poor (<10%). This was due to the highly acid-consuming nature of the battery waste. Multistage leaching with the graphite electrolyte solution improved leach yields overall, but the electrodes corroded over time. Though yields obtained with both electrolyte leach solutions were low when compared to the 4 M HCl control, there still remains potential to optimise the conditions for the generation of the acidic anolyte solution and the solubilisation of valuable metals from the LIB waste. A preliminary value proposition indicated that the process has the potential to be economically feasible if leach yields can be improved, especially based on the value of recoverable cobalt and lithium. Copyright © 2018 Elsevier Ltd. All rights reserved.

The development of a new type of rechargeable batteries based on hybrid electrolytes.

PubMed

Zhou, Haoshen; Wang, Yonggang; Li, Huiqiao; He, Ping

2010-09-24

Lithium ion batteries (LIBs), which have the highest energy density among all currently available rechargeable batteries, have recently been considered for use in hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and pure electric vehicles (PEV). A major challenge in this effort is to increase the energy density of LIBs to satisfy the industrial needs of HEVs, PHEVs, and PEVs. Recently, new types of lithium-air and lithium-copper batteries that employ hybrid electrolytes have attracted significant attention; these batteries are expected to succeed lithium ion batteries as next-generation power sources. Herein, we review the concept of hybrid electrolytes, as well as their advantages and disadvantages. In addition, we examine new battery types that use hybrid electrolytes.

Lithium and an EPAC-specific inhibitor ESI-09 synergistically suppress pancreatic cancer cell proliferation and survival.

PubMed

Wang, Xinshuo; Luo, Cheng; Cheng, Xiaodong; Lu, Meiling

2017-07-01

Our previous studies showed that while lithium suppresses proliferation and induces apoptosis in pancreatic cancer cells, the inhibition of exchange proteins directly activated by cyclic adenosine monophosphate (cAMP) (EPAC)1 blocks pancreatic cancer cell migration and invasion. In this study, we further investigated the combinatory effects of lithium and EPAC-specific inhibitor (ESI)-09, an EPAC-specific inhibitor, on pancreatic cancer cell proliferation and viability, and explored whether lithium synergistically cooperates with EPAC inhibition in suppressing pancreatic cancer cell tumorigenicity. The cell viability of pancreatic cancer cell lines PANC-1 and MiaPaCa-2 was measured after 48 h of incubation with different dose combination of lithium and ESI-09. Flow cytometric analysis was carried out to further verify the impact of lithium and ESI-09 upon PANC-1 cell proliferation and apoptosis. To investigate the mechanism that the effects generated by lithium and ESI-09 on PANC-1 cells, the intracellular cAMP level was measured by an ELISA-based cAMP immunoassay. Our data showed that lithium and ESI-09 synergistically inhibit pancreatic cancer cell growth and survival. Furthermore, our results revealed a novel mechanism in which the synergism between lithium and ESI-09 is not mediated by the inhibitory effect of lithium toward GSK3β, but by lithium's ability to suppress cAMP/protein kinase A signaling. © The Author 2017. Published by Oxford University Press on behalf of the Institute of Biochemistry and Cell Biology, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Lithium Ion Recognition with Nanofluidic Diodes through Host-Guest Complexation in Confined Geometries.

PubMed

Ali, Mubarak; Ahmed, Ishtiaq; Ramirez, Patricio; Nasir, Saima; Mafe, Salvador; Niemeyer, Christof M; Ensinger, Wolfgang

2018-05-15

The lithium ion recognition is receiving significant attention because of its application in pharmaceuticals, lubricants and, especially, in energy technology. We present a nanofluidic device for specific lithium ion recognition via host-guest complexation in a confined environment. A lithium-selective receptor molecule, the aminoethyl-benzo-12-crown-4 (BC12C4-NH 2 ), is designed and functionalized on single conical nanopores in polyethylene terephthalate (PET) membranes. The native carboxylic acid groups on the pore walls are covalently linked with the crown ether moieties and the process is monitored from the changes in the current-voltage ( I- V) curves. The B12-crown-4 moieties are known to specifically bind with lithium ions and when the modified pore is exposed to different alkali metal chloride solutions separately, significant changes in the ion current and rectification are only observed for lithium chloride. This fact suggests the generation of positively charged B12C4-Li + complexes on the pore surface. Furthermore, the nanofluidic diode is able to recognize the lithium ion even in the presence of high concentrations of potassium ions in the external electrolyte solution. Thus, this nanodevice suggests a strategy to miniaturize nanofluidic porous systems for efficient recognition, extraction, and separation of lithium from raw materials.

Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li-S Batteries with High Sulfur Mass Loading.

PubMed

Chen, Lin; Huang, Zhennan; Shahbazian-Yassar, Reza; Libera, Joseph A; Klavetter, Kyle C; Zavadil, Kevin R; Elam, Jeffrey W

2018-02-28

Lithium metal is considered the "holy grail" of next-generation battery anodes. However, severe parasitic reactions at the lithium-electrolyte interface deplete the liquid electrolyte and the uncontrolled formation of high surface area and dendritic lithium during cycling causes rapid capacity fading and battery failure. Engineering a dendrite-free lithium metal anode is therefore critical for the development of long-life batteries using lithium anodes. In this study, we deposit a conformal, organic/inorganic hybrid coating, for the first time, directly on lithium metal using molecular layer deposition (MLD) to alleviate these problems. This hybrid organic/inorganic film with high cross-linking structure can stabilize lithium against dendrite growth and minimize side reactions, as indicated by scanning electron microscopy. We discovered that the alucone coating yielded several times longer cycle life at high current rates compared to the uncoated lithium and achieved a steady Coulombic efficiency of 99.5%, demonstrating that the highly cross-linking structured material with great mechanical properties and good flexibility can effectively suppress dendrite formation. The protected Li was further evaluated in lithium-sulfur (Li-S) batteries with a high sulfur mass loading of ∼5 mg/cm 2 . After 140 cycles at a high current rate of ∼1 mA/cm 2 , alucone-coated Li-S batteries delivered a capacity of 657.7 mAh/g, 39.5% better than that of a bare lithium-sulfur battery. These findings suggest that flexible coating with high cross-linking structure by MLD is effective to enable lithium protection and offers a very promising avenue for improved performance in the real applications of Li-S batteries.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Westmont, IL; Amine, Khalil [Downers Grove, IL

2012-01-31

Primary and secondary Li-ion and lithium-metal based electrochemical cell systems. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plasticized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Bolingbrook, IL; Amine, Khalil [Downers Grove, IL

2008-06-24

Primary and secondary Li-ion and lithium-metal based electrochemical cell system. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plastized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

Anode material for lithium batteries

DOEpatents

Belharouak, Ilias [Bolingbrook, IL; Amine, Khalil [Oak Brook, IL

2011-04-05

Primary and secondary Li-ion and lithium-metal based electrochemical cell systems. The suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of respective cell, or to the cell itself whether it be a liquid, a solid- or plasticized polymer electrolyte system. The gas suppression additives are primarily based on unsaturated hydrocarbons.

The effects of sulfide composition on the solubility of sulfur in coexisting silicate melts

NASA Astrophysics Data System (ADS)

Smythe, Duane; Wood, Bernard; Kiseeva, Ekaterina

2016-04-01

The extent to which sulfur dissolves in silicate melts saturated in an immiscible sulfide phase is a fundamental question in igneous petrology and plays a primary role in the generation of magmatic ore deposits, volcanic degassing and planetary differentiation. Terrestrial sulfide melts often contain over 20 weight percent Ni + Cu, however, most experimental studies investigating sulfur solubility in silicate melt have been primarily concerned with the effects of silicate melt composition, and pure FeS has been use as the immiscible sulfide melt (O'Neill and Mavrogenes, 2002; Li and Ripley, 2005). To investigation of the effects of sulfide composition, in addition to those of temperature, pressure and silicate melt composition, on sulfur solubility in silicate melts, we have carried out a series of experiments done at pressures between 1.5 and 3 GPa and temperatures from 1400 to 1800C over a range of compositions of both the silicate and sulfide melt. We find that the solubility of sulfur in silicate melts drops significantly with the substitution of Ni and Cu for Fe in the immiscible sulfide melt, decreasing by approximately 40% at mole fractions of NiS + Cu2S of 0.4. Combining our results with those from the previous studies investigating sulfur solubility in silicate melts we have also found that solubility increases with increasing temperature and decreases pressure. These results show that without considering the composition of the immiscible sulfide phase the sulfur content of silicate melts can be significantly overestimated. This may serve to explain the relatively low sulfur concentrations in MORB melts, which previous models predict to be undersaturated in a sulfide phase despite showing chemical and textural evidence for sulfide saturation. Li, C. & Ripley, E. M. (2005). Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits. Mineralium Deposita 40, 218-230. O'Neill, H. S. C. & Mavrogenes, J. A. (2002). The Sulfide Capacity and the Sulfur Content at Sulfide Saturation of Silicate Melts at 1400°C and 1 bar. Journal of Petrology 43, 1049-1087.

Liquid-phase chemical hydrogen storage: catalytic hydrogen generation under ambient conditions.

PubMed

Jiang, Hai-Long; Singh, Sanjay Kumar; Yan, Jun-Min; Zhang, Xin-Bo; Xu, Qiang

2010-05-25

There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

Evaluation of domain randomness in periodically poled lithium niobate by diffraction noise measurement.

PubMed

Dwivedi, Prashant Povel; Choi, Hee Joo; Kim, Byoung Joo; Cha, Myoungsik

2013-12-16

Random duty-cycle errors (RDE) in ferroelectric quasi-phase-matching (QPM) devices not only affect the frequency conversion efficiency, but also generate non-phase-matched parasitic noise that can be detrimental to some applications. We demonstrate an accurate but simple method for measuring the RDE in periodically poled lithium niobate. Due to the equivalence between the undepleted harmonic generation spectrum and the diffraction pattern from the QPM grating, we employed linear diffraction measurement which is much simpler than tunable harmonic generation experiments [J. S. Pelc, et al., Opt. Lett.36, 864-866 (2011)]. As a result, we could relate the RDE for the QPM device to the relative noise intensity between the diffraction orders.

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-01-01

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-03-01

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

Technologies for Extracting Valuable Metals and Compounds from Geothermal Fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harrison, Stephen

2014-04-30

Executive Summary Simbol Materials studied various methods of extracting valuable minerals from geothermal brines in the Imperial Valley of California, focusing on the extraction of lithium, manganese, zinc and potassium. New methods were explored for managing the potential impact of silica fouling on mineral extraction equipment, and for converting silica management by-products into commercial products.` Studies at the laboratory and bench scale focused on manganese, zinc and potassium extraction and the conversion of silica management by-products into valuable commercial products. The processes for extracting lithium and producing lithium carbonate and lithium hydroxide products were developed at the laboratory scale andmore » scaled up to pilot-scale. Several sorbents designed to extract lithium as lithium chloride from geothermal brine were developed at the laboratory scale and subsequently scaled-up for testing in the lithium extraction pilot plant. Lithium The results of the lithium studies generated the confidence for Simbol to scale its process to commercial operation. The key steps of the process were demonstrated during its development at pilot scale: 1. Silica management. 2. Lithium extraction. 3. Purification. 4. Concentration. 5. Conversion into lithium hydroxide and lithium carbonate products. Results show that greater than 95% of the lithium can be extracted from geothermal brine as lithium chloride, and that the chemical yield in converting lithium chloride to lithium hydroxide and lithium carbonate products is greater than 90%. The product purity produced from the process is consistent with battery grade lithium carbonate and lithium hydroxide. Manganese and zinc Processes for the extraction of zinc and manganese from geothermal brine were developed. It was shown that they could be converted into zinc metal and electrolytic manganese dioxide after purification. These processes were evaluated for their economic potential, and at the present time Simbol Materials is evaluating other products with greater commercial value. Potassium Silicotitanates, zeolites and other sorbents were evaluated as potential reagents for the extraction of potassium from geothermal brines and production of potassium chloride (potash). It was found that zeolites were effective at removing potassium but the capacity of the zeolites and the form that the potassium is in does not have economic potential. Iron-silica by-product The conversion of iron-silica by-product produced during silica management operations into more valuable materials was studied at the laboratory scale. Results indicate that it is technically feasible to convert the iron-silica by-product into ferric chloride and ferric sulfate solutions which are precursors to a ferric phosphate product. However, additional work to purify the solutions is required to determine the commercial viability of this process. Conclusion Simbol Materials is in the process of designing its first commercial plant based on the technology developed to the pilot scale during this project. The investment in the commercial plant is hundreds of millions of dollars, and construction of the commercial plant will generate hundreds of jobs. Plant construction will be completed in 2016 and the first lithium products will be shipped in 2017. The plant will have a lithium carbonate equivalent production capacity of 15,000 tonnes per year. The gross revenues from the project are expected to be approximately $ 80 to 100 million annually. During this development program Simbol grew from a company of about 10 people to over 60 people today. Simbol is expected to employ more than 100 people once the plant is constructed. Simbol Materials’ business is scalable in the Imperial Valley region because there are eleven geothermal power plants already in operation, which allows Simbol to expand its business from one plant to multiple plants. Additionally, the scope of the resource is vast in terms of potential products such as lithium, manganese and zinc and potentially potassium.« less

The Pulsed Fission-Fusion (PUFF) Concept for Deep Space Exploration and Terrestrial Power Generation

NASA Technical Reports Server (NTRS)

Adams, Robert; Cassibry, Jason; Schillo, Kevin

2017-01-01

This team is exploring a modified Z-pinch geometry as a propulsion system, imploding a liner of liquid lithium onto a pellet containing both fission and fusion fuel. The plasma resulting from the fission and fusion burn expands against a magnetic nozzle, for propulsion, or a magnetic confinement system, for terrestrial power generation. There is considerable synergy in the concept; the lithium acts as a temporary virtual cathode, and adds reaction mass for propulsion. Further, the lithium acts as a radiation shield against generated neutrons and gamma rays. Finally, the density profile of the column can be tailored using the lithium sheath. Recent theoretical and experimental developments (e.g. tailored density profile in the fuel injection, shear stabilization, and magnetic shear stabilization) have had great success in mitigating instabilities that have plagued previous fusion efforts. This paper will review the work in evaluating the pellet sizes and z-pinch conditions for optimal PuFF propulsion. Trades of pellet size and composition with z-pinch power levels and conditions for the tamper and lithium implosion are evaluated. Current models, both theoretical and computational, show that a z-pinch can ignite a small (1 cm radius) fission-fusion target with significant yield. Comparison is made between pure fission and boosted fission targets. Performance is shown for crewed spacecraft for high speed Mars round trip missions and near interstellar robotic missions. The PuFF concept also offers a solution for terrestrial power production. PuFF can, with recycling of the effluent, achieve near 100% burnup of fission fuel, providing a very attractive power source with minimal waste. The small size of PuFF relative to today's plants enables a more distributed power network and less exposure to natural or man-made disruptions.

Strong texturing of lithium metal in batteries

DOE PAGES

Shi, Feifei; Pei, Allen; Vailionis, Arturas; ...

2017-10-30

Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type ofmore » additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO 3 and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. In conclusion, this understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.« less

Strong texturing of lithium metal in batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Feifei; Pei, Allen; Vailionis, Arturas

Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type ofmore » additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO 3 and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. In conclusion, this understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.« less

Magmatic evolution of a Cordilleran flare-up and its role in the creation of silicic crust.

PubMed

Ward, Kevin M; Delph, Jonathan R; Zandt, George; Beck, Susan L; Ducea, Mihai N

2017-08-22

The role of magmatic processes as a significant mechanism for the generation of voluminous silicic crust and the development of Cordilleran plateaus remains a lingering question in part because of the inherent difficulty in quantifying plutonic volumes. Despite this difficulty, a growing body of independently measured plutonic-to-volcanic ratios suggests the volume of plutonic material in the crust related to Cordilleran magmatic systems is much larger than is previously expected. To better examine the role of crustal magmatic processes and its relationship to erupted material in Cordilleran systems, we present a continuous high-resolution crustal seismic velocity model for an ~800 km section of the active South American Cordillera (Puna Plateau). Although the plutonic-to-volcanic ratios we estimate vary along the length of the Puna Plateau, all ratios are larger than those previously reported (~30:1 compared to 5:1) implying that a significant volume of intermediate to silicic plutonic material is generated in the crust of the central South American Cordillera. Furthermore, as Cordilleran-type margins have been common since the onset of modern plate tectonics, our findings suggest that similar processes may have played a significant role in generating and/or modifying large volumes of continental crust, as observed in the continents today.

Effect of Energetic Plasma Flux on Flowing Liquid Lithium Surfaces

NASA Astrophysics Data System (ADS)

Kalathiparambil, Kishor; Jung, Soonwook; Christenson, Michael; Fiflis, Peter; Xu, Wenyu; Szott, Mathew; Ruzic, David

2014-10-01

An operational liquid lithium system with steady state flow driven by thermo-electric magneto-hydrodynamic force and capable of constantly refreshing the plasma exposed surface have been demonstrated at U of I. To evaluate the system performance in reactor relevant conditions, specifically to understand the effect of disruptive plasma events on the performance of the liquid metal PFCs, the setup was integrated to a pulsed plasma generator. A coaxial plasma generator drives the plasma towards a theta pinch which preferentially heats the ions, simulating ELM like flux, and the plasma is further guided towards the target chamber which houses the flowing lithium system. The effect of the incident flux is examined using diagnostic tools including triple Langmuir probe, calorimeter, rogowski coils, Ion energy analyzers, and fast frame spectral image acquisition with specific optical filters. The plasma have been well characterized and a density of ~1021 m-3, with electron temperature ~10 - 20 eV is measured, and final plasma velocities of 34 - 74 kms-1 have been observed. Calorimetric measurements using planar molybdenum targets indicate a maximum plasma energy (with 6 kV plasma gun and 20 kV theta pinch) of 0.08 MJm-2 with plasma divergence effects resulting in marginal reduction of 40 +/- 23 J in plasma energy. Further results from the other diagnostic tools, using the flowing lithium targets and the planar targets coated with lithium will be presented. DOE DE-SC0008587.

Entire mesodermal mantle behaves as Spemann's organizer in dorsoanterior enhanced Xenopus laevis embryos

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kao, K.R.; Elinson, R.P.

1988-05-01

The body plan of Xenopus laevis can be respecified by briefly exposing early cleavage stage embryos to lithium. Such embryos develop exaggerated dorsoanterior structures such as a radial eye and cement gland. In this paper, we demonstrate that the enhanced dorsoanterior phenotype results from an overcommitment of mesoderm to dorsoanterior mesoderm. Histological and immunohistochemical observations reveal that the embryos have a greatly enlarged notochord with very little muscle tissue. In addition, they develop a radial, beating heart, suggesting that lithium also specifies anterior mesoderm and pharyngeal endoderm. Randomly oriented diametrically opposed marginal zone grafts from lithium-treated embryos, when transplanted intomore » ultraviolet (uv)-irradiated axis-deficient hosts, rescue dorsal axial structures. These transplantation experiments demonstrate that the entire marginal zone of the early gastrula consists of presumptive dorsal mesoderm. Vital dye marking experiments also indicate that the entire marginal zone maps to the prominent proboscis that is composed of chordamesoderm and represents the long axis of the embryo. These results suggest that lithium respecifies the mesoderm of Xenopus laevis embryos so that it differentiates into the Spemann organizer. We suggest that the origin of the dorsoanterior enhanced phenotypes generated by lithium and the dorsoanterior deficient phenotypes generated by uv irradiation are due to relative quantities of organizer. Our evidence demonstrates the existence of a continuum of body plan phenotypes based on this premise.« less

Toxic fluoride gas emissions from lithium-ion battery fires.

PubMed

Larsson, Fredrik; Andersson, Petra; Blomqvist, Per; Mellander, Bengt-Erik

2017-08-30

Lithium-ion battery fires generate intense heat and considerable amounts of gas and smoke. Although the emission of toxic gases can be a larger threat than the heat, the knowledge of such emissions is limited. This paper presents quantitative measurements of heat release and fluoride gas emissions during battery fires for seven different types of commercial lithium-ion batteries. The results have been validated using two independent measurement techniques and show that large amounts of hydrogen fluoride (HF) may be generated, ranging between 20 and 200 mg/Wh of nominal battery energy capacity. In addition, 15-22 mg/Wh of another potentially toxic gas, phosphoryl fluoride (POF 3 ), was measured in some of the fire tests. Gas emissions when using water mist as extinguishing agent were also investigated. Fluoride gas emission can pose a serious toxic threat and the results are crucial findings for risk assessment and management, especially for large Li-ion battery packs.

Wear, strength, modulus and hardness of CAD/CAM restorative materials.

PubMed

Lawson, Nathaniel C; Bansal, Ritika; Burgess, John O

2016-11-01

To measure the mechanical properties of several CAD/CAM materials, including lithium disilicate (e.max CAD), lithium silicate/zirconia (Celtra Duo), 3 resin composites (Cerasmart, Lava Ultimate, Paradigm MZ100), and a polymer infiltrated ceramic (Enamic). CAD/CAM blocks were sectioned into 2.5mm×2.5mm×16mm bars for flexural strength and elastic modulus testing and 4mm thick blocks for hardness and wear testing. E.max CAD and half the Celtra Duo specimens were treated in a furnace. Flexural strength specimens (n=10) were tested in a three-point bending fixture. Vickers microhardness (n=2, 5 readings per specimen) was measured with a 1kg load and 15s dwell time. The CAD/CAM materials as well as labial surfaces of human incisors were mounted in the UAB wear device. Cusps of human premolars were mounted as antagonists. Specimens were tested for 400,000 cycles at 20N force, 2mm sliding distance, 1Hz frequency, 24°C, and 33% glycerin lubrication. Volumetric wear and opposing enamel wear were measured with non-contact profilometry. Data were analyzed with 1-way ANOVA and Tukey post-hoc analysis (alpha=0.05). Specimens were observed with SEM. Properties were different for each material (p<0.01). E.max CAD and Celtra Duo were generally stronger, stiffer, and harder than the other materials. E.max CAD, Celtra Duo, Enamic, and enamel demonstrated signs of abrasive wear, whereas Cerasmart, Lava Ultimate, Paradigm MZ100 demonstrated signs of fatigue. Resin composite and resin infiltrated ceramic materials have demonstrated adequate wear resistance for load bearing restorations, however, they will require at least similar material thickness as lithium disilicate restorations due to their strength. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Materials Challenges and Opportunities of Lithium-ion Batteries for Electrical Energy Storage

NASA Astrophysics Data System (ADS)

Manthiram, Arumugam

2011-03-01

Electrical energy storage has emerged as a topic of national and global importance with respect to establishing a cleaner environment and reducing the dependence on foreign oil. Batteries are the prime candidates for electrical energy storage. They are the most viable near-term option for vehicle applications and the efficient utilization of intermittent energy sources like solar and wind. Lithium-ion batteries are attractive for these applications as they offer much higher energy density than other rechargeable battery systems. However, the adoption of lithium-ion battery technology for vehicle and stationary storage applications is hampered by high cost, safety concerns, and limitations in energy, power, and cycle life, which are in turn linked to severe materials challenges. This presentation, after providing an overview of the current status, will focus on the physics and chemistry of new materials that can address these challenges. Specifically, it will focus on the design and development of (i) high-capacity, high-voltage layered oxide cathodes, (ii) high-voltage, high-power spinel oxide cathodes, (iii) high-capacity silicate cathodes, and (iv) nano-engineered, high-capacity alloy anodes. With high-voltage cathodes, a critical issue is the instability of the electrolyte in contact with the highly oxidized cathode surface and the formation of solid-electrolyte interfacial (SEI) layers that degrade the performance. Accordingly, surface modification of cathodes with nanostructured materials and self-surface segregation during the synthesis process to suppress SEI layer formation and enhance the energy, power, and cycle life will be emphasized. With the high-capacity alloy anodes, a critical issue is the huge volume change occurring during the charge-discharge process and the consequent poor cycle life. Dispersion of the active alloy nanoparticles in an inactive metal oxide-carbon matrix to mitigate this problem and realize long cycle life will be presented.

Li4SiO4-Based Artificial Passivation Thin Film for Improving Interfacial Stability of Li Metal Anodes.

PubMed

Kim, Ji Young; Kim, A-Young; Liu, Guicheng; Woo, Jae-Young; Kim, Hansung; Lee, Joong Kee

2018-03-14

An amorphous SiO 2 (a-SiO 2 ) thin film was developed as an artificial passivation layer to stabilize Li metal anodes during electrochemical reactions. The thin film was prepared using an electron cyclotron resonance-chemical vapor deposition apparatus. The obtained passivation layer has a hierarchical structure, which is composed of lithium silicide, lithiated silicon oxide, and a-SiO 2 . The thickness of the a-SiO 2 passivation layer could be varied by changing the processing time, whereas that of the lithium silicide and lithiated silicon oxide layers was almost constant. During cycling, the surface of the a-SiO 2 passivation layer is converted into lithium silicate (Li 4 SiO 4 ), and the portion of Li 4 SiO 4 depends on the thickness of a-SiO 2 . A minimum overpotential of 21.7 mV was observed at the Li metal electrode at a current density of 3 mA cm -2 with flat voltage profiles, when an a-SiO 2 passivation layer of 92.5 nm was used. The Li metal with this optimized thin passivation layer also showed the lowest charge-transfer resistance (3.948 Ω cm) and the highest Li ion diffusivity (7.06 × 10 -14 cm 2 s -1 ) after cycling in a Li-S battery. The existence of the Li 4 SiO 4 artificial passivation layer prevents the corrosion of Li metal by suppressing Li dendritic growth and improving the ionic conductivity, which contribute to the low charge-transfer resistance and high Li ion diffusivity of the electrode.

Melt segregation from silicic crystal mushes: a critical appraisal of possible mechanisms and their microstructural record

NASA Astrophysics Data System (ADS)

Holness, Marian B.

2018-06-01

One of the outstanding problems in understanding the behavior of intermediate-to-silicic magmatic systems is the mechanism(s) by which large volumes of crystal-poor rhyolite can be extracted from crystal-rich mushy storage zones in the mid-deep crust. The mechanisms commonly invoked are hindered settling, micro-settling, and compaction. The concept of micro-settling involves extraction of grains from a crystal framework during Ostwald ripening and has been shown to be non-viable in the metallic systems for which it was originally proposed. Micro-settling is also likely to be insignificant in silicic mushes, because ripening rates are slow for quartz and plagioclase, contact areas between grains in a crystal mush are likely to be large, and abundant low-angle grain boundaries promote grain coalescence rather than ripening. Published calculations of melt segregation rates by hindered settling (Stokes settling in a crystal-rich system) neglect all but fluid dynamical interactions between particles. Because tabular silicate minerals are likely to form open, mechanically coherent, frameworks at porosities as high as 75%, settling of single crystals is only likely in very melt-rich systems. Gravitationally-driven viscous compaction requires deformation of crystals by either dissolution-reprecipitation or dislocation creep. There is, as yet, no reported microstructural evidence of extensive, syn-magmatic, internally-generated, viscous deformation in fully solidified silicic plutonic rocks. If subsequent directed searches do not reveal clear evidence for internally-generated buoyancy-driven melt segregation processes, it is likely that other factors, such as rejuvenation by magma replenishment, gas filter-pressing, or externally-imposed stress during regional deformation, are required to segregate large volumes of crystal-poor rhyolitic liquids from crustal mushy zones.

Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

NASA Astrophysics Data System (ADS)

Verdolotti, Letizia; Liguori, Barbara; Capasso, Ilaria; Caputo, Domenico; Lavorgna, Marino; Iannace, Salvatore

2014-05-01

Organic-inorganic hybrid foams based on an alkali alumino-silicate matrix were prepared by using different foaming methods. Initially, the synthesis of an inorganic matrix by using aluminosilicate particles, activated through a sodium silicate solution, was performed at room temperature. Subsequently the viscous paste was foamed by using three different methods. In the first method, gaseous hydrogen produced by the oxidization of Si powder in an alkaline media, was used as blowing agent to generate gas bubbles in the paste. In the second method, the porous structure was generated by mixing the paste with a "meringue" type of foam previously prepared by whipping, under vigorous stirring, a water solution containing vegetal proteins as surfactants. In the third method, a combination of these two methods was employed. The foamed systems were consolidated for 24 hours at 40°C and then characterized by FTIR, X-Ray diffraction, scanning electron microscopy (SEM) and compression tests. Low density foams (˜500 Kg/m3) with good cellular structure and mechanical properties were obtained by combining the "meringue" approach with the use of the chemical blowing agent based on Si.

Partitioning of light lithophile elements during basalt eruptions on Earth and application to Martian shergottites

NASA Astrophysics Data System (ADS)

Edmonds, Marie

2015-02-01

An enigmatic record of light lithophile element (LLE) zoning in pyroxenes in basaltic shergottite meteorites, whereby LLE concentrations decrease dramatically from the cores to the rims, has been interpreted as being due to partitioning of LLE into a hydrous vapor during magma ascent to the surface on Mars. These trends are used as evidence that Martian basaltic melts are water-rich (McSween et al., 2001). Lithium and boron are light lithophile elements (LLE) that partition into volcanic minerals and into vapor from silicate melts, making them potential tracers of degassing processes during magma ascent to the surface of Earth and of other planets. While LLE degassing behavior is relatively well understood for silica-rich melts, where water and LLE concentrations are relatively high, very little data exists for LLE abundance, heterogeneity and degassing in basaltic melts. The lack of data hampers interpretation of the trends in the shergottite meteorites. Through a geochemical study of LLE, volatile and trace elements in olivine-hosted melt inclusions from Kilauea Volcano, Hawaii, it can be demonstrated that lithium behaves similarly to the light to middle rare Earth elements during melting, magma mixing and fractionation. Considerable heterogeneity in lithium and boron is inherited from mantle-derived primary melts, which is dominant over the fractionation and degassing signal. Lithium and boron are only very weakly volatile in basaltic melt erupted from Kilauea Volcano, with vapor-melt partition coefficients <0.1. Degassing of LLE is further inhibited at high temperatures. Pyroxene and associated melt inclusion LLE concentrations from a range of volcanoes are used to quantify lithium pyroxene-melt partition coefficients, which correlate negatively with melt H2O content, ranging from 0.13 at low water contents to <0.08 at H2O contents >4 wt%. The observed terrestrial LLE partitioning behavior is extrapolated to Martian primitive melts through modeling. The zoning observed in the shergottite pyroxenes is only consistent with degassing of LLE from a Martian melt near its liquidus temperature if the vapor-melt partition coefficient was an order of magnitude larger than observed on Earth. The range in LLE and trace elements observed in shergottite pyroxenes are instead consistent with concurrent mixing and fractionation of heterogeneous melts from the mantle.

Lithium vapor/aerosol studies. Interim summary report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whitlow, G.A.; Bauerle, J.E.; Down, M.G.

1979-04-01

The temperature/cover gas pressure regime, in which detectable lithium aerosol is formed in a static system has been mapped for argon and helium cover gases using a portable He--Ne laser device. At 538/sup 0/C (1000/sup 0/F), lithium aerosol particles were observed over the range 0.5 to 20 torr and 2 to 10 torr for argon and helium respectively. The experimental conditions in this study were more conducive to aerosol formation than in a fusion reactor. In the real reactor system, very high intensity mechanical and thermal disturbances will be made to the liquid lithium. These disturbances, particularly transient increases inmore » lithium vapor pressure appear to be capable of producing high concentrations of optically-dense aerosol. A more detailed study is, therefore, proposed using the basic information generated in these preliminary experiments, as a starting point. Areas recommended include the kinetics of aerosol formation and the occurrence of supersaturated vapor during rapid vapor pressure transients, and also the effect of lithium agitation (falls, jets, splashing, etc.) on aerosol formation.« less

A novel class of halogen-free, super-conductive lithium argyrodites: Synthesis and characterization

NASA Astrophysics Data System (ADS)

Schneider, Holger; Du, Hui; Kelley, Tracy; Leitner, Klaus; ter Maat, Johan; Scordilis-Kelley, Chariclea; Sanchez-Carrera, Roel; Kovalev, Igor; Mudalige, Anoma; Kulisch, Jörn; Safont-Sempere, Marina M.; Hartmann, Pascal; Weiβ, Thomas; Schneider, Ling; Hinrichsen, Bernd

2017-10-01

Solid electrolytes are the core components for many next generation lithium battery concepts such as all-solid-state batteries (ASSB) or batteries based on metallic lithium anodes protected by a ceramic or composite passivation layer. Therefore, the search for new solid state Li-ion conductors with superior properties and improved electrochemical stabilities remains of high interest. In this work, the synthesis of a new class of silicon-containing, sulfide-based lithium-ion conductors is reported. Very good conductivities of up to ∼2.0-3.0·10-3 S/cm could be achieved for compositions such as Li22SiP2S18, among the highest for silicon sulfide containing materials. Based on the recorded powder XRD diffraction patterns and simulations it could be confirmed that they constitute novel members of the argyrodite family of sulfide lithium-ion conductors. The cubic high-temperature modification of such argyrodites with high lithium-ion conductivity can therefore be stabilized by implementation of silicon into the lattice, while additional doping with halogen atoms is not necessary.

Biological and Organic Chemical Decomposition of Silicates. Chapter 7.2

NASA Technical Reports Server (NTRS)

Silverman, M. P.

1979-01-01

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geo- chemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth surface.

Biological and Organic Chemical Decomposition of Silicates. Chapter 7.2

NASA Technical Reports Server (NTRS)

Sliverman, M. P.

1979-01-01

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geochemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth's surface.

The Distribution and Composition Characteristics of Siliceous Rocks from Qinzhou Bay-Hangzhou Bay Joint Belt, South China: Constraint on the Tectonic Evolution of Plates in South China

PubMed Central

Li, Hongzhong; Zhai, Mingguo; Zhang, Lianchang; Zhou, Yongzhang; Yang, Zhijun; He, Junguo; Liang, Jin; Zhou, Liuyu

2013-01-01

The Qinzhou Bay-Hangzhou Bay joint belt is a significant tectonic zone between the Yangtze and Cathaysian plates, where plentiful hydrothermal siliceous rocks are generated. Here, the authors studied the distribution of the siliceous rocks in the whole tectonic zone, which indicated that the tensional setting was facilitating the development of siliceous rocks of hydrothermal genesis. According to the geochemical characteristics, the Neopalaeozoic siliceous rocks in the north segment of the Qinzhou Bay-Hangzhou Bay joint belt denoted its limited width. In comparison, the Neopalaeozoic Qinzhou Bay-Hangzhou Bay joint belt was diverse for its ocean basin in the different segments and possibly had subduction only in the south segment. The ocean basin of the north and middle segments was limited in its width without subduction and possibly existed as a rift trough that was unable to resist the terrigenous input. In the north segment of the Qinzhou Bay-Hangzhou Bay joint belt, the strata of hydrothermal siliceous rocks in Dongxiang copper-polymetallic ore deposit exhibited alternative cycles with the marine volcanic rocks, volcanic tuff, and metal sulphide. These sedimentary systems were formed in different circumstances, whose alternative cycles indicated the release of internal energy in several cycles gradually from strong to weak. PMID:24302882

Discrete dipole approximation models of chrystalline forsterite: Applications to cometary crystalline silicates

NASA Astrophysics Data System (ADS)

Lindsay, Sean Stephen

The shape, size, and composition of crystalline silicates observed in comet comae and external proto-planetary disks are indicative of the formation and evolution of the dust grains during the processes of planetary formation. In this dissertation, I present the 3 -- 40 mum absorption efficiencies( Qabs) of irregularly shaped forsterite crystals computed with the discrete dipole approximation (DDA) code DDSCAT developed by Draine and Flatau and run on the NASA Advanced Supercomputing facility Pleiades. An investigation of grain shapes ranging from spheroidal to irregular indicate that the strong spectral features from forsterite are sensitive to grain shape and are potentially degenerate with the effects of crystal solid state composition (Mg-content). The 10, 11, 18, 23, and 33.5 mum features are found to be the most crystal shape sensitive and should be avoided in determining Mg-content. The distinct spectral features for the three shape classes are connected with crystal formation environment using a condensation experiment by (Kobatake et al., 2008). The condensation experiment demonstrates that condensed forsterite crystal shapes are dependent on the condensation environmental temperature. I generate DDSCAT target analog shapes to the condensed crystal shapes. These analog shapes are represented by the three shape classes: 1) equant, 2) a, c-columns, and 3) b-shortened platelets. Each of these shape classes exhibit distinct spectral features that can be used to interpret grain shape characteristics from 8 --- 40 mum spectroscopy of astronomical objects containing crystalline silicates. Synthetic spectral energy distributions (SEDs) of the coma of Hale-Bopp at rh = 2.8 AU are generated by thermally modeling the flux contributions of 5 mineral species present in comets. The synthetic SEDs are constrained using a chi2- minimization technique. The mineral species are amorphous carbon, amorphous pyroxene, amorphous olivine, crystalline enstatite, and crystalline forsterite. Using the DDSCAT computed absorption efficiencies for a large variety of forsterite crystal shapes, which are computed for 66 grain sizes between 0.1 -- 5.0 mum, the flux contribution of irregularly shaped forsterite is computed. The forsterite flux contribution is then summed with the amorphous and crystalline enstatite contributions to generate the total synthetic SED. The DDSCAT forsterite grain shape synthetic SEDs reveal that the crystalline silicates in the coma of Hale-Bopp are irregular in shape with two distinct shape characteristics related to specific formation mechanisms: 1) equant grains with sharp ( ≲ 90°) angles between the faces, edges, and vertices that formed as high temperature condensates in the inner 1 -- 3 AU radial region of the Solar System's protoplanetary disk; and 2) c-shortened platelet shapes that likely formed from collisional processing of the crystals. The 8 -- 40 mum silicate spectral features of Hale-Bopp's coma are compared to the silicate spectral features of the comae of 17P/Holmes during 2007 outburst and 9P/Tempel 1 during the Deep Impact experiment to show that the silicate features with crystalline resonances are remarkably similar. The similarity in silicate spectral features suggests that the grain populations in the comae of these comets are similar in shape, size, and compositon. However, Hale-Bopp is a nearly isotropic comet (NIC) that dynamically came from the Oort cloud, and 17P and 9P are ecliptic comets (ECs) that dynamically came from the Scattered Disk. The different dynamical source regions yet similar silicate (amorphous and crystalline) grain populations suggest that ECs and NICs innately have similar grains and that the typically weaker silicate features of ECs are an effect of the surface grains becoming compacted with numerous perihelion passages. Hence, the differences in silicate between ECs and NICs are the result of grain structure and not grain composition. (Abstract shortened by UMI.)

Laser or charged-particle-beam fusion reactor with direct electric generation by magnetic flux compression

DOEpatents

Lasche, George P.

1988-01-01

A high-power-density laser or charged-particle-beam fusion reactor system maximizes the directed kinetic energy imparted to a large mass of liquid lithium by a centrally located fusion target. A fusion target is embedded in a large mass of lithium, of sufficient radius to act as a tritium breeding blanket, and provided with ports for the access of beam energy to implode the target. The directed kinetic energy is converted directly to electricity with high efficiency by work done against a pulsed magnetic field applied exterior to the lithium. Because the system maximizes the blanket thickness per unit volume of lithium, neutron-induced radioactivities in the reaction chamber wall are several orders of magnitude less than is typical of other fusion reactor systems.

Lithium Ion Batteries in Electric Drive Vehicles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pesaran, Ahmad A.

2016-05-16

This research focuses on the technical issues that are critical to the adoption of high-energy-producing lithium Ion batteries. In addition to high energy density / high power density, this publication considers performance requirements that are necessary to assure lithium ion technology as the battery format of choice for electrified vehicles. Presentation of prime topics includes: long calendar life (greater than 10 years); sufficient cycle life; reliable operation under hot and cold temperatures; safe performance under extreme conditions; end-of-life recycling. To achieve aggressive fuel economy standards, carmakers are developing technologies to reduce fuel consumption, including hybridization and electrification. Cost and affordabilitymore » factors will be determined by these relevant technical issues which will provide for the successful implementation of lithium ion batteries for application in future generations of electrified vehicles.« less

Laser or charged-particle-beam fusion reactor with direct electric generation by magnetic flux compression

DOEpatents

Lasche, G.P.

1987-02-20

A high-power-density-laser or charged-particle-beam fusion reactor system maximizes the directed kinetic energy imparted to a large mass of liquid lithium by a centrally located fusion target. A fusion target is embedded in a large mass of lithium, of sufficient radius to act as a tritium breeding blanket, and provided with ports for the access of beam energy to implode the target. The directed kinetic energy is converted directly to electricity with high efficiency by work done against a pulsed magnetic field applied exterior to the lithium. Because the system maximizes the blanket thickness per unit volume of lithium, neutron-induced radioactivities in the reaction chamber wall are several orders of magnitude less than is typical of other fusion reactor systems. 25 figs.

Nanostructured metal oxide-based materials as advanced anodes for lithium-ion batteries.

PubMed

Wu, Hao Bin; Chen, Jun Song; Hng, Huey Hoon; Lou, Xiong Wen David

2012-04-21

The search for new electrode materials for lithium-ion batteries (LIBs) has been an important way to satisfy the ever-growing demands for better performance with higher energy/power densities, improved safety and longer cycle life. Nanostructured metal oxides exhibit good electrochemical properties, and they are regarded as promising anode materials for high-performance LIBs. In this feature article, we will focus on three different categories of metal oxides with distinct lithium storage mechanisms: tin dioxide (SnO(2)), which utilizes alloying/dealloying processes to reversibly store/release lithium ions during charge/discharge; titanium dioxide (TiO(2)), where lithium ions are inserted/deinserted into/out of the TiO(2) crystal framework; and transition metal oxides including iron oxide and cobalt oxide, which react with lithium ions via an unusual conversion reaction. For all three systems, we will emphasize that creating nanomaterials with unique structures could effectively improve the lithium storage properties of these metal oxides. We will also highlight that the lithium storage capability can be further enhanced through designing advanced nanocomposite materials containing metal oxides and other carbonaceous supports. By providing such a rather systematic survey, we aim to stress the importance of proper nanostructuring and advanced compositing that would result in improved physicochemical properties of metal oxides, thus making them promising negative electrodes for next-generation LIBs.

The boron and lithium isotopic composition of mid-ocean ridge basalts and the mantle

NASA Astrophysics Data System (ADS)

Marschall, Horst R.; Wanless, V. Dorsey; Shimizu, Nobumichi; Pogge von Strandmann, Philip A. E.; Elliott, Tim; Monteleone, Brian D.

2017-06-01

A global selection of 56 mid-ocean ridge basalt (MORB) glasses were analysed for Li and B abundances and isotopic compositions. Analytical accuracy and precision of analyses constitute an improvement over previously published MORB data and allow a more detailed discussion of the Li and B systematics of the crust-mantle system. Refined estimates for primitive mantle abundances ([ Li ] = 1.39 ± 0.10 μg/g and [ B ] = 0.19 ± 0.02 μg/g) and depleted mantle abundances ([ Li ] = 1.20 ± 0.10 μg/g and [ B ] = 0.077 ± 0.010 μg/g) are presented based on mass balance and on partial melting models that utilise observed element ratios in MORB. Assimilation of seawater (or brine) or seawater-altered material beneath the ridge, identified by high Cl / K , causes significant elevation of MORB δ11 B and variable elevation in δ7 Li . The B isotope ratio is, hence, identified as a reliable indicator of assimilation in MORB and values higher than -6‰ are strongly indicative of shallow contamination of the magma. The global set of samples investigated here were produced at various degrees of partial melting and include depleted and enriched MORB from slow and fast-spreading ridge segments with a range of radiogenic isotope signatures and trace element compositions. Uncontaminated (low- Cl / K) MORB show no significant boron isotope variation at the current level of analytical precision, and hence a homogenous B isotopic composition of δ11 B = - 7.1 ± 0.9 ‰ (mean of six ridge segments; 2SD). Boron isotope fractionation during mantle melting and basalt fractionation likely is small, and this δ11 B value reflects the B isotopic composition of the depleted mantle and the bulk silicate Earth, probably within ±0.4‰. Our sample set shows a mean δ7 Li = + 3.5 ± 1.0 ‰ (mean of five ridge segments; 2SD), excluding high- Cl / K samples. A significant variation of 1.0-1.5‰ exists among various ridge segments and among samples within individual ridge segments, but this variation is unrelated to differentiation, assimilation or mantle source indicators, such as radiogenic isotopes or trace elements. It, therefore, seems likely that kinetic fractionation of Li isotopes during magma extraction, transport and storage may generate δ7 Li excursions in MORB. No mantle heterogeneities, such as those generated by deeply recycled subducted materials, are invoked in the interpretation of the Li and B isotope data presented here, in contrast to previous work on smaller data sets. Lithium and boron budgets for the silicate Earth are presented that are based on isotope and element mass balance. A refined estimate for the B isotopic composition of the bulk continental crust is given as δ11 B = - 9.1 ± 2.4 ‰ . Mass balance allows the existence of recycled B reservoirs in the deep mantle, but these are not required. However, mass balance among the crust, sediments and seawater shows enrichment of 6 Li in the surface reservoirs, which requires the existence of 7 Li -enriched material in the mantle. This may have formed by the subduction of altered oceanic crust since the Archaean.

Few-cycle solitons and supercontinuum generation with cascaded quadratic nonlinearities in unpoled lithium niobate ridge waveguides.

PubMed

Guo, Hairun; Zeng, Xianglong; Zhou, Binbin; Bache, Morten

2014-03-01

Formation and interaction of few-cycle solitons in a lithium niobate ridge waveguide are numerically investigated. The solitons are created through a cascaded phase-mismatched second-harmonic generation process, which induces a dominant self-defocusing Kerr-like nonlinearity on the pump pulse. The inherent material self-focusing Kerr nonlinearity is overcome over a wide wavelength range, and self-defocusing solitons are supported from 1100 to 1900 nm, covering the whole communication band. Single cycle self-compressed solitons and supercontinuum generation spanning 1.3 octaves are observed when pumped with femtosecond nanojoule pulses at 1550 nm. The waveguide is not periodically poled, as quasi-phase-matching would lead to detrimental nonlinear effects impeding few-cycle soliton formation.

Continuous-wave sodium D2 resonance radiation generated in single-pass sum-frequency generation with periodically poled lithium niobate.

PubMed

Yue, J; She, C-Y; Williams, B P; Vance, J D; Acott, P E; Kawahara, T D

2009-04-01

With two cw single-mode Nd:YAG lasers at 1064 and 1319 nm and a periodically poled lithium niobate crystal, 11 mW of 2 kHz/100 ms bandwidth single-mode tunable 589 nm cw radiation has been detected using single-pass sum-frequency generation. The demonstrated conversion efficiency is approximately 3.2%[W(-1) cm(-1)]. This compact solid-state light source has been used in a solid-state-dye laser hybrid sodium fluorescence lidar transmitter to measure temperatures and winds in the upper atmosphere (80-105 km); it is being implemented into the transmitter of a mobile all-solid-state sodium temperature and wind lidar under construction.

Laser processing of thick Li(NiMnCo)O2 electrodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Rakebrandt, J.-H.; Smyrek, P.; Zheng, Y.; Seifert, H. J.; Pfleging, W.

2017-02-01

Lithium-ion batteries became the most promising types of mobile energy storage devices due to their high gravimetric and volumetric capacity, high cycle life-time, and low self-discharge. Nowadays, the cathode material lithium nickel manganese cobalt oxide (NMC) is one of the most widely used cathode material in commercial lithium-ion batteries due to many advantages such as high energy density (>150 Wh kg-1) on cell level, high power density (650 W kg-1 @ 25 °C and 50 % Depth of Discharge) [1], high specific capacity (163 mAh g-1) [2], high rate capability and good thermal stability in the fully charged state. However, in order to meet the requirements for the increasing demand for rechargeable high energy batteries, nickel-rich NMC electrodes with specific capacities up to 210 mAh g-1 seem to be the next generation cathodes which can reach on cell level desired energy densities higher than 250 Wh kg-1 [3]. Laser-structuring now enables to combine both concepts, high power and high energy lithium-ion batteries. For this purpose, lithium nickel manganese cobalt oxide cathodes were produced via tape casting containing 85-90 wt% of active material with a film thickness of 50-260 μm. The specific capacities were measured using galvanostatic measurements for different types of NMC with varying nickel, manganese and cobalt content at different charging/discharging currents ("C-rates"). An improved lithium-ion diffusion kinetics due to an increased active surface area could be achieved by laser-assisted generating of three dimensional architectures. Cells with unstructured and structured cathodes were compared. Ultrafast laser ablation was used in order to avoid a thermal impact to the material. It was shown that laser structuring of electrode materials leads to a significant improvement in electrochemical performance, especially at high charging and discharging C-rates.

High-power electron beam tests of a liquid-lithium target and characterization study of (7)Li(p,n) near-threshold neutrons for accelerator-based boron neutron capture therapy.

PubMed

Halfon, S; Paul, M; Arenshtam, A; Berkovits, D; Cohen, D; Eliyahu, I; Kijel, D; Mardor, I; Silverman, I

2014-06-01

A compact Liquid-Lithium Target (LiLiT) was built and tested with a high-power electron gun at Soreq Nuclear Research Center (SNRC). The target is intended to demonstrate liquid-lithium target capabilities to constitute an accelerator-based intense neutron source for Boron Neutron Capture Therapy (BNCT) in hospitals. The lithium target will produce neutrons through the (7)Li(p,n)(7)Be reaction and it will overcome the major problem of removing the thermal power >5kW generated by high-intensity proton beams, necessary for sufficient therapeutic neutron flux. In preliminary experiments liquid lithium was flown through the target loop and generated a stable jet on the concave supporting wall. Electron beam irradiation demonstrated that the liquid-lithium target can dissipate electron power densities of more than 4kW/cm(2) and volumetric power density around 2MW/cm(3) at a lithium flow of ~4m/s, while maintaining stable temperature and vacuum conditions. These power densities correspond to a narrow (σ=~2mm) 1.91MeV, 3mA proton beam. A high-intensity proton beam irradiation (1.91-2.5MeV, 2mA) is being commissioned at the SARAF (Soreq Applied Research Accelerator Facility) superconducting linear accelerator. In order to determine the conditions of LiLiT proton irradiation for BNCT and to tailor the neutron energy spectrum, a characterization of near threshold (~1.91MeV) (7)Li(p,n) neutrons is in progress based on Monte-Carlo (MCNP and Geant4) simulation and on low-intensity experiments with solid LiF targets. In-phantom dosimetry measurements are performed using special designed dosimeters based on CR-39 track detectors. © 2013 Elsevier Ltd. All rights reserved.

Development of a high-brightness, applied-B lithium extraction ion diode for inertial confinement fusion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cuneo, M.E.; Adams, R.G.; Armijo, J.

The light ion fusion program is pursuing the development of a high brightness lithium ion beam on the SABRE accelerator at Sandia (6 MV, 0.25 MA). This will require the integration of at least three conditions: (1) an active, pre-formed, uniform lithium plasma ion source, (2) modification of the electron sheath distribution in the AK gap, and (3) mitigation of undesired electrode plasmas. These experiments represent the first attempt to combine these three conditions in a lithium ion diode. The primary goal is the production of a lithium beam with a micro-divergence at peak ion power of {le} 20 mrad,more » about half the previous value achieved on SABRE. A secondary goal is reduction of the impedance collapse rate. The primary approach is a laser-produced lithium plasma generated with 10 ns YAG laser illumination of LiAg films. Laser fluences of 0.5--1.0 J/cm{sup 2} appear to be satisfactory to generate a dense, highly ionized, low temperature plasma. An ohmically-generally, thin-film ion source is also being developed as a backup, longer term approach. Small-scale experiments are performed to study each ion source in detail, prior to fielding on the accelerator. Pre-formed anode plasmas allow the use of high magnetic fields (Vcrit/V {ge} 2) and limiters which slow the onset of a high beam divergence electromagnetic instability and slow impedance collapse. High magnetic fields will be achieved with 1.8 MJ capacitor banks. An extensive array of in-situ electrode cleaning techniques have been developed to limit parasitic ion loads and impedance collapse from electrode contaminant plasma formation. Advanced ion beam, electron sheath and spectroscopic AK gap diagnostics have also been developed.« less

Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Jie; Liao, Lei; Shi, Feifei

Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a “reaction in the beaker”, avoiding direct handling of highly toxic fluorine gas. Formore » lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm 2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li–O 2 and Li–S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, Li xSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows Li xSi to be stable in humid air (~40% relative humidity). Furthermore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.« less

Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability

DOE PAGES

Zhao, Jie; Liao, Lei; Shi, Feifei; ...

2017-07-26

Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a “reaction in the beaker”, avoiding direct handling of highly toxic fluorine gas. Formore » lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm 2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li–O 2 and Li–S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, Li xSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows Li xSi to be stable in humid air (~40% relative humidity). Furthermore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.« less

Simultaneously phase-matched second- and third-harmonic generation from 1.55 microm radiation in annealed proton-exchanged periodically poled lithium niobate waveguides.

PubMed

Marangoni, M; Lobino, M; Ramponi, R

2006-09-15

Third-harmonic generation (THG) in the cw regime from C-band radiation was achieved in annealed proton-exchanged periodically poled lithium niobate (PPLN) waveguides. By suitable design of fabrication parameters and operating conditions, quasi-phase-matching (QPM) is obtained simultaneously for the second-harmonic generation process (omega-->2omega, first-order QPM) and for the sum-frequency-generation process (omega+2omega-->3omega, third-order QPM), which provides the third harmonic of the pump field. The high overlap between the field profiles of the interacting modes--TM00 at omega and TM10 at 2omega and 3omega--results in what is believed to be the highest ever reported normalized conversion efficiency for THG from telecommunication wavelengths, equal to 0.72%W(-2) cm(-4).

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

PubMed Central

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic −EO− based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm−1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions. PMID:26791572

Change the morphology of lithium oxides by Nd-Yag laser beam to use as a sand in water-cooled reactors

NASA Astrophysics Data System (ADS)

Karwi, Abbas Ali Mahmmod

2018-04-01

Laser has many attractive specifications which made it adaptable for material processing. Laser has been taken as a modern heat treatment source to prevent the formation of non-protective oxide layer with intensity equals to (1.31×105 w/cm2), lasing time equals to (300 µs), wave length equals to (1.063 µm), and the spot radius equals to (125 µm). Lithium is depleted through the conventional heat treatment processes. The main factors affected on lithium depletion are temperature and time. Lithium kept as a solid solution at casting method. Micro hardness of the affected zone reaches to acceptable values for various ageing times and hardening depths. The main conventional heat treatment processes are; homogenization, solution heat treatment, and ageing. Alloys prepared with the specific amounts of lithium concentration (2-2.5%). Oxides with different shapes are formed. Temperature distribution, heating, and cooling rates used externally and internally to see the effect of pulse generation by laser on bulk body.

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic -EO- based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm-1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

State-of-the-art characterization techniques for advanced lithium-ion batteries

NASA Astrophysics Data System (ADS)

Lu, Jun; Wu, Tianpin; Amine, Khalil

2017-03-01

To meet future needs for industries from personal devices to automobiles, state-of-the-art rechargeable lithium-ion batteries will require both improved durability and lowered costs. To enhance battery performance and lifetime, understanding electrode degradation mechanisms is of critical importance. Various advanced in situ and operando characterization tools developed during the past few years have proven indispensable for optimizing battery materials, understanding cell degradation mechanisms, and ultimately improving the overall battery performance. Here we review recent progress in the development and application of advanced characterization techniques such as in situ transmission electron microscopy for high-performance lithium-ion batteries. Using three representative electrode systems—layered metal oxides, Li-rich layered oxides and Si-based or Sn-based alloys—we discuss how these tools help researchers understand the battery process and design better battery systems. We also summarize the application of the characterization techniques to lithium-sulfur and lithium-air batteries and highlight the importance of those techniques in the development of next-generation batteries.

New insights into negative effects of lithium on sea urchin Paracentrotus lividus embryos

PubMed Central

Ruocco, Nadia; Costantini, Maria; Santella, Luigia

2016-01-01

The diffuse use of lithium in a number of industrial processes has produced a significant contamination of groundwater and surface water with it. The increased use of lithium has generated only scarce studies on its concentrations in ambient waters and on its effects on aquatic organisms. Only few contributions have focused on the toxicity of lithium in marine organisms (such as marine animals, algae and vegetables), showing that the toxic effect depends on the animal species. In the present study we describe the morphological and the molecular effects of lithium chloride (LiCl), using the sea urchin Paracentrotus lividus as a model organism. We show that LiCl, if added to the eggs before fertilization, induces malformations in the embryos in a dose-dependent manner. We have also followed by RT qPCR the expression levels of thirty seven genes (belonging to different classes of functional processes, such as stress, development, differentiation, skeletogenesis and detoxifications) to identify the molecular targets of LiCl. This study opens new perspectives for the understanding of the mechanism of action of lithium on marine organisms. The findings may also have relevance outside the world of marine organisms since lithium is widely prescribed for the treatment of human bipolar disorders. PMID:27562248

New insights into negative effects of lithium on sea urchin Paracentrotus lividus embryos.

PubMed

Ruocco, Nadia; Costantini, Maria; Santella, Luigia

2016-08-26

The diffuse use of lithium in a number of industrial processes has produced a significant contamination of groundwater and surface water with it. The increased use of lithium has generated only scarce studies on its concentrations in ambient waters and on its effects on aquatic organisms. Only few contributions have focused on the toxicity of lithium in marine organisms (such as marine animals, algae and vegetables), showing that the toxic effect depends on the animal species. In the present study we describe the morphological and the molecular effects of lithium chloride (LiCl), using the sea urchin Paracentrotus lividus as a model organism. We show that LiCl, if added to the eggs before fertilization, induces malformations in the embryos in a dose-dependent manner. We have also followed by RT qPCR the expression levels of thirty seven genes (belonging to different classes of functional processes, such as stress, development, differentiation, skeletogenesis and detoxifications) to identify the molecular targets of LiCl. This study opens new perspectives for the understanding of the mechanism of action of lithium on marine organisms. The findings may also have relevance outside the world of marine organisms since lithium is widely prescribed for the treatment of human bipolar disorders.

New insights into negative effects of lithium on sea urchin Paracentrotus lividus embryos

NASA Astrophysics Data System (ADS)

Ruocco, Nadia; Costantini, Maria; Santella, Luigia

2016-08-01

The diffuse use of lithium in a number of industrial processes has produced a significant contamination of groundwater and surface water with it. The increased use of lithium has generated only scarce studies on its concentrations in ambient waters and on its effects on aquatic organisms. Only few contributions have focused on the toxicity of lithium in marine organisms (such as marine animals, algae and vegetables), showing that the toxic effect depends on the animal species. In the present study we describe the morphological and the molecular effects of lithium chloride (LiCl), using the sea urchin Paracentrotus lividus as a model organism. We show that LiCl, if added to the eggs before fertilization, induces malformations in the embryos in a dose-dependent manner. We have also followed by RT qPCR the expression levels of thirty seven genes (belonging to different classes of functional processes, such as stress, development, differentiation, skeletogenesis and detoxifications) to identify the molecular targets of LiCl. This study opens new perspectives for the understanding of the mechanism of action of lithium on marine organisms. The findings may also have relevance outside the world of marine organisms since lithium is widely prescribed for the treatment of human bipolar disorders.

Investigation of enhanced forward and backward anti-stokes Raman signals in lithium niobate waveguides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Da; Hong, Pengda; Ding, Yujie J., E-mail: yding300@gmail.com

2015-07-07

We have observed enhancements of the anti-Stokes Raman signals generated in lithium niobate waveguides in the forward and backward configurations by at least one order of magnitude under the pump power of the microwatt level. These output signals were measured using a single photon detector. The forward and backward propagating anti-Stokes signals exhibited different spectral features.

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

PubMed

Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

2018-02-19

The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

Absorption generator for solar-powered air-conditioner

NASA Technical Reports Server (NTRS)

Lowen, D. J.; Murray, J. G.

1977-01-01

Device passes solar-heated water through coils. Hot lithium Bromide/Water solution leaves through central stand-pipe, and water vapor leaves through refrigerant outlet at top. Matching generation temperature to collector efficiency helps cut costs.

A Self-Healing Aqueous Lithium-Ion Battery.

PubMed

Zhao, Yang; Zhang, Ye; Sun, Hao; Dong, Xiaoli; Cao, Jingyu; Wang, Lie; Xu, Yifan; Ren, Jing; Hwang, Yunil; Son, In Hyuk; Huang, Xianliang; Wang, Yonggang; Peng, Huisheng

2016-11-07

Flexible lithium-ion batteries are critical for the next-generation electronics. However, during the practical application, they may break under deformations such as twisting and cutting, causing their failure to work or even serious safety problems. A new family of all-solid-state and flexible aqueous lithium ion batteries that can self-heal after breaking has been created by designing aligned carbon nanotube sheets loaded with LiMn 2 O 4 and LiTi 2 (PO 4 ) 3 nanoparticles on a self-healing polymer substrate as electrodes, and a new kind of lithium sulfate/sodium carboxymethylcellulose serves as both gel electrolyte and separator. The specific capacity, rate capability, and cycling performance can be well maintained after repeated cutting and self-healing. These self-healing batteries are demonstrated to be promising for wearable devices. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Lithium Oxygen Battery Using a Glyme Electrolyte and Carbon Nanotubes.

PubMed

Carbone, Lorenzo; Moro, Paolo Tomislav; Gobet, Mallory; Munoz, Stephen; Devany, Matthew; Greenbaum, Steven G; Hassoun, Jusef

2018-05-16

The lithium oxygen battery has a theoretical energy density potentially meeting the challenging requirements of electric vehicles. However, safety concerns and short lifespan hinder its application in practical systems. In this work, we show a cell configuration, including a multiwalled carbon nanotube electrode and a low flammability glyme electrolyte, capable of hundreds of cycles without signs of decay. Nuclear magnetic resonance and electrochemical tests confirm the suitability of the electrolyte in a practical battery, whereas morphological and structural aspects revealed by electron microscopy and X-ray diffraction demonstrate the reversible formation and dissolution of lithium peroxide during the electrochemical process. The enhanced cycle life of the cell and the high safety of the electrolyte suggest the lithium oxygen battery herein reported as a viable system for the next generation of high-energy applications.

The largest volcanic eruptions on Earth

NASA Astrophysics Data System (ADS)

Bryan, Scott E.; Peate, Ingrid Ukstins; Peate, David W.; Self, Stephen; Jerram, Dougal A.; Mawby, Michael R.; Marsh, J. S. (Goonie); Miller, Jodie A.

2010-10-01

Large igneous provinces (LIPs) are sites of the most frequently recurring, largest volume basaltic and silicic eruptions in Earth history. These large-volume (> 1000 km 3 dense rock equivalent) and large-magnitude (> M8) eruptions produce areally extensive (10 4-10 5 km 2) basaltic lava flow fields and silicic ignimbrites that are the main building blocks of LIPs. Available information on the largest eruptive units are primarily from the Columbia River and Deccan provinces for the dimensions of flood basalt eruptions, and the Paraná-Etendeka and Afro-Arabian provinces for the silicic ignimbrite eruptions. In addition, three large-volume (675-2000 km 3) silicic lava flows have also been mapped out in the Proterozoic Gawler Range province (Australia), an interpreted LIP remnant. Magma volumes of > 1000 km 3 have also been emplaced as high-level basaltic and rhyolitic sills in LIPs. The data sets indicate comparable eruption magnitudes between the basaltic and silicic eruptions, but due to considerable volumes residing as co-ignimbrite ash deposits, the current volume constraints for the silicic ignimbrite eruptions may be considerably underestimated. Magma composition thus appears to be no barrier to the volume of magma emitted during an individual eruption. Despite this general similarity in magnitude, flood basaltic and silicic eruptions are very different in terms of eruption style, duration, intensity, vent configuration, and emplacement style. Flood basaltic eruptions are dominantly effusive and Hawaiian-Strombolian in style, with magma discharge rates of ~ 10 6-10 8 kg s -1 and eruption durations estimated at years to tens of years that emplace dominantly compound pahoehoe lava flow fields. Effusive and fissural eruptions have also emplaced some large-volume silicic lavas, but discharge rates are unknown, and may be up to an order of magnitude greater than those of flood basalt lava eruptions for emplacement to be on realistic time scales (< 10 years). Most silicic eruptions, however, are moderately to highly explosive, producing co-current pyroclastic fountains (rarely Plinian) with discharge rates of 10 9-10 11 kg s -1 that emplace welded to rheomorphic ignimbrites. At present, durations for the large-magnitude silicic eruptions are unconstrained; at discharge rates of 10 9 kg s -1, equivalent to the peak of the 1991 Mt Pinatubo eruption, the largest silicic eruptions would take many months to evacuate > 5000 km 3 of magma. The generally simple deposit structure is more suggestive of short-duration (hours to days) and high intensity (~ 10 11 kg s -1) eruptions, perhaps with hiatuses in some cases. These extreme discharge rates would be facilitated by multiple point, fissure and/or ring fracture venting of magma. Eruption frequencies are much elevated for large-magnitude eruptions of both magma types during LIP-forming episodes. However, in basalt-dominated provinces (continental and ocean basin flood basalt provinces, oceanic plateaus, volcanic rifted margins), large magnitude (> M8) basaltic eruptions have much shorter recurrence intervals of 10 3-10 4 years, whereas similar magnitude silicic eruptions may have recurrence intervals of up to 10 5 years. The Paraná-Etendeka province was the site of at least nine > M8 silicic eruptions over an ~ 1 Myr period at ~ 132 Ma; a similar eruption frequency, although with a fewer number of silicic eruptions is also observed for the Afro-Arabian Province. The huge volumes of basaltic and silicic magma erupted in quick succession during LIP events raises several unresolved issues in terms of locus of magma generation and storage (if any) in the crust prior to eruption, and paths and rates of ascent from magma reservoirs to the surface. Available data indicate four end-member magma petrogenetic pathways in LIPs: 1) flood basalt magmas with primitive, mantle-dominated geochemical signatures (often high-Ti basalt magma types) that were either transferred directly from melting regions in the upper mantle to fissure vents at surface, or resided temporarily in reservoirs in the upper mantle or in mafic underplate thereby preventing extensive crustal contamination or crystallisation; 2) flood basalt magmas (often low-Ti types) that have undergone storage at lower ± upper crustal depths resulting in crustal assimilation, crystallisation, and degassing; 3) generation of high-temperature anhydrous, crystal-poor silicic magmas (e.g., Paraná-Etendeka quartz latites) by large-scale AFC processes involving lower crustal granulite melting and/or basaltic underplate remelting; and 4) rejuvenation of upper-crustal batholiths (mainly near-solidus crystal mush) by shallow intrusion and underplating by mafic magma providing thermal and volatile input to produce large volumes of crystal-rich (30-50%) dacitic to rhyolitic magma and for ignimbrite-producing eruptions, well-defined calderas up to 80 km diameter (e.g., Fish Canyon Tuff model), and which characterise of some silicic eruptions in silicic LIPs.

A case of the tail wagging the dog? Reverse weathering and Earth's CO2 thermostat.

NASA Astrophysics Data System (ADS)

Higgins, J. A.

2017-12-01

Feedbacks between climate, the global carbon cycle, and the chemistry of seawater stabilize Earth's surface temperature on geologic timescales and are likely responsible for its habitability over billions of years of Earth history. The most important component of the geologic carbon cycle is the precipitation and burial of carbonate sediments. The amount of carbonate sediment produced depends, in turn, on the alkalinity generated during silicate weathering less the amount consumed during the formation of secondary clay minerals both on the continents and in the ocean. In marine enviroments this process, often referred to as reverse weathering, consumes seawater alkalinity (and cations) via reaction with degraded Al-silicate minerals. Because these reactions constitute a sink of seawater alkalinity, changes in the amount of reverse weathering will lead to imbalances between alkalinity sources and sinks. The net effect is that on timescales greater than the timescale of carbonate compensation (< 10 kyr), changes in reverse weathering will lead to changes in the rate of continental silicate weathering through the dependence of continental silicate weathering on atmospheric CO2 and climate. This mechanism is capable of changing rates of continental silicate weathering without changing either the rate of volcanic outgassing or the rate constant for continental silicate weathering (i.e. through mountain-building or the exposure of different rock types) and as a result represents a unique way of modulating the global carbon cycle and Earth's climate on geologic timescales.

Development of liquid-lithium film jet-flow for the target of (7)Li(p,n)(7)Be reactions for BNCT.

PubMed

Kobayashi, Tooru; Miura, Kuniaki; Hayashizaki, Noriyosu; Aritomi, Masanori

2014-06-01

A feasibility study on liquid lithium target in the form of a flowing film was performed to evaluate its potential use as a neutron generation target of (7)Li(p,n)(7)Be reaction in BNCT. The target is a windowless-type flowing film on a concave wall. Its configuration was adapted for a proton beam which is 30mm in diameter and with energy and current of up to 3MeV and 20mA, respectively. The flowing film of liquid lithium was 0.6mm in thickness, 50mm in width and 50mm in length. The shapes of the nozzle and concave back wall, which create a stable flowing film jet, were decided based on water experiments. A lithium hydrodynamic experiment was performed to observe the stability of liquid lithium flow behavior. The flowing film of liquid lithium was found to be feasible at temperatures below the liquid lithium boiling saturation of 342°C at the surface pressure of 1×10(-3)Pa. Using a proto-type liquid lithium-circulating loop for BNCT, the stability of the film flow was confirmed for velocities up to 30m/s at 220°C and 250°C in vacuum at a pressure lower than 10(-3) Pa. It is expected that for practical use, a flowing liquid lithium target of a windowless type can solve the problem of radiation damage and target cooling. Copyright © 2013 Elsevier Ltd. All rights reserved.

Aqueous Dispersions of Silica Stabilized with Oleic Acid Obtained by Green Chemistry.

PubMed

Nistor, Cristina Lavinia; Ianchis, Raluca; Ghiurea, Marius; Nicolae, Cristian-Andi; Spataru, Catalin-Ilie; Culita, Daniela Cristina; Pandele Cusu, Jeanina; Fruth, Victor; Oancea, Florin; Donescu, Dan

2016-01-05

The present study describes for the first time the synthesis of silica nanoparticles starting from sodium silicate and oleic acid (OLA). The interactions between OLA and sodium silicate require an optimal OLA/OLANa molar ratio able to generate vesicles that can stabilize silica particles obtained by the sol-gel process of sodium silicate. The optimal molar ratio of OLA/OLANa can be ensured by a proper selection of OLA and respectively of sodium silicate concentration. The titration of sodium silicate with OLA revealed a stabilization phenomenon of silica/OLA vesicles and the dependence between their average size and reagent's molar ratio. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) measurements emphasized the successful synthesis of silica nanoparticles starting from renewable materials, in mild condition of green chemistry. By grafting octadecyltrimethoxysilane on the initial silica particles, an increased interaction between silica particles and the OLA/OLANa complex was achieved. This interaction between the oleyl and octadecyl chains resulted in the formation of stable gel-like aqueous systems. Subsequently, olive oil and an oleophylic red dye were solubilized in these stable aqueous systems. This great dispersing capacity of oleosoluble compounds opens new perspectives for future green chemistry applications. After the removal of water and of the organic chains by thermal treatment, mesoporous silica was obtained.

Multi-Wall Carbon Nanotubes as Lithium Nanopipettes and SPM Probes

NASA Astrophysics Data System (ADS)

Larson, Jonathan; Bharath, Satyaveda; Cullen, William; Reutt-Robey, Janice

2014-03-01

A multi-walled carbon nanotube (MWCNT) - terminated SPM cantilever, was utilized to perform nanolithography and surface diffusion measurements on a thin film of vapor-deposited lithium atop a silicon (111) substrate under ultra-high vacuum conditions. In these investigations the MWCNT tip was shown to act as both a lithium nanopipette and a probe for non-contact atomic force microscopy (NC-AFM) measurements. With the application of appropriate bias conditions, the MWCNT could site-selectively extract (expel) nano-scale amounts of lithium from (to) the sample surface. Depressions, mounds, and spikes were generated on the surface in this way and were azimuthally symmetric about the selected point of pipetting. Following lithium transfer to/from the substrate, the MWCNT pipette-induced features were sequentially imaged with NC-AFM using the MWCNT as the probe. Vacancy pits of ca. 300 nm diameter and 1.5 nm depth were observed to decay on a timescale of hours at room temperature, through diffusion-limited decay processes. A continuum model was utilized to simulate the island decay rates, and the lithium surface diffusion coefficient of D =7.5 (+/-1.3)*10-15 cm2/s was extracted. U.S. Department of Energy Award Number DESC0001160.

The corrosion protection of AA2024-T3 aluminium alloy by leaching of lithium-containing salts from organic coatings.

PubMed

Visser, Peter; Liu, Yanwen; Zhou, Xiaorong; Hashimoto, Teruo; Thompson, George E; Lyon, Stuart B; van der Ven, Leendert G J; Mol, Arjan J M C; Terryn, Herman A

2015-01-01

Lithium carbonate and lithium oxalate were incorporated as leachable corrosion inhibitors in model organic coatings for the protection of AA2024-T3. The coated samples were artificially damaged with a scribe. It was found that the lithium-salts are able to leach from the organic coating and form a protective layer in the scribe on AA2024-T3 under neutral salt spray conditions. The present paper shows the first observation and analysis of these corrosion protective layers, generated from lithium-salt loaded organic coatings. The scribed areas were examined by scanning and transmission electron microscopy before and after neutral salt spray exposure (ASTM-B117). The protective layers typically consist of three different layered regions, including a relatively dense layer near the alloy substrate, a porous middle layer and a flake-shaped outer layer, with lithium uniformly distributed throughout all three layers. Scanning electron microscopy and white light interferometry surface roughness measurements demonstrate that the formation of the layer occurs rapidly and, therefore provides an effective inhibition mechanism. Based on the observation of this work, a mechanism is proposed for the formation of these protective layers.

Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid.

PubMed

Zeng, Xianlai; Li, Jinhui; Shen, Bingyu

2015-09-15

With the booming of consumer electronics (CE) and electric vehicle (EV), a large number of spent lithium-ion battery (LIBs) have been generated worldwide. Resource depletion and environmental concern driven from the sustainable industry of CE and EV have motivated spent LIBs should be recovered urgently. However, the conventional process combined with leaching, precipitating, and filtering was quite complicated to recover cobalt and lithium from spent LIBs. In this work, we developed a novel recovery process, only combined with oxalic acid leaching and filtering. When the optimal parameters for leaching process is controlled at 150 min retention time, 95 °C heating temperature, 15 g L(-1) solid-liquid ratio, and 400 rpm rotation rate, the recovery rate of lithium and cobalt from spent LIBs can reach about 98% and 97%, respectively. Additionally, we also tentatively discovered the leaching mechanism of lithium cobalt oxide (LiCoO2) using oxalic acid, and the leaching order of the sampling LiCoO2 of spent LIBs. All the obtained results can contribute to a short-cut and high-efficiency process of spent LIBs recycling toward a sound closed-loop cycle. Copyright © 2015 Elsevier B.V. All rights reserved.

Catalytic activity in lithium-treated core–shell MoO x/MoS 2 nanowires

DOE PAGES

Cummins, Dustin R.; Martinez, Ulises; Kappera, Rajesh; ...

2015-09-22

Significant interest has grown in the development of earth-abundant and efficient catalytic materials for hydrogen generation. Layered transition metal dichalcogenides present opportunities for efficient electrocatalytic systems. Here, we report the modification of 1D MoO x/MoS 2 core–shell nanostructures by lithium intercalation and the corresponding changes in morphology, structure, and mechanism of H 2 evolution. The 1D nanowires exhibit significant improvement in H 2 evolution properties after lithiation, reducing the hydrogen evolution reaction (HER) onset potential by ~50 mV and increasing the generated current density by ~600%. The high electrochemical activity in the nanowires results from disruption of MoS 2 layersmore » in the outer shell, leading to increased activity and concentration of defect sites. This is in contrast to the typical mechanism of improved catalysis following lithium exfoliation, i.e., crystal phase transformation. As a result, these structural changes are verified by a combination of Raman and X-ray photoelectron spectroscopy (XPS).« less

Directing the Lithium-Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries.

PubMed

Lee, Chang-Wook; Pang, Quan; Ha, Seungbum; Cheng, Lei; Han, Sang-Don; Zavadil, Kevin R; Gallagher, Kevin G; Nazar, Linda F; Balasubramanian, Mahalingam

2017-06-28

The lithium-sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium-sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium-sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium-sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. This discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation-dissolution chemistries, lithium-sulfur and beyond.

Reaction mechanisms for the limited reversibility of Li-O 2 chemistry in organic carbonate electrolytes

NASA Astrophysics Data System (ADS)

Xu, Wu; Xu, Kang; Viswanathan, Vilayanur V.; Towne, Silas A.; Hardy, John S.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Wang, Deyu; Zhang, Ji-Guang

The Li-O 2 chemistry in nonaqueous liquid carbonate electrolytes and the underlying reason for its limited reversibility was systematically investigated. X-ray diffraction data showed that regardless of discharge depth lithium alkylcarbonates (lithium propylenedicarbonate (LPDC), or lithium ethylenedicarbonate (LEDC), with other related derivatives) and lithium carbonate (Li 2CO 3) are constantly the main discharge products, while lithium peroxide (Li 2O 2) or lithium oxide (Li 2O) is hardly detected. These lithium alkylcarbonates are generated from the reductive decomposition of the corresponding carbonate solvents initiated by the attack of superoxide radical anions. More significantly, in situ gas chromatography/mass spectroscopy analysis revealed that Li 2CO 3 and Li 2O cannot be oxidized even when charged to 4.6 V vs. Li/Li +, while LPDC, LEDC and Li 2O 2 are readily oxidized, with CO 2 and CO released from LPDC and LEDC and O 2 evolved from Li 2O 2. Therefore, the apparent reversibility of Li-O 2 chemistry in an organic carbonate-based electrolyte is actually an unsustainable process that consists of (1) the formation of lithium alkylcarbonates through the reductive decomposition of carbonate solvents during discharging and (2) the subsequent oxidation of these same alkylcarbonates during charging. Therefore, a stable electrolyte that does not lead to an irreversible by-product formation during discharging and charging is necessary for truly rechargeable Li-O 2 batteries.

Partial dissolution of ACQ-treated wood in lithium chloride/N-methyl-2-pyrrolidinone: Separation of copper from potential lignocellulosic feedstocks

Treesearch

Thomas L. Eberhardt; Stan Lebow; Karen G. Reed

2012-01-01

A cellulose solvent system based on lithium chloride (LiCl) in N-methyl-2-pyrrolidinone (NMP) was used to assess the merits of partial dissolutions of coarsely ground wood samples. Alkaline Copper Quaternary (ACQ)-treated pine wood was of particular interest for treatment given the potential to generate a copper- rich stream apart from solid and/or liquid...

Exceptional Lithium Storage in a Co(OH) 2 Anode: Hydride Formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Hyunchul; Choi, Woon Ih; Jang, Yoonjung

Current lithium ion battery technology is tied in with conventional reaction mechanisms such as insertion, conversion, and alloying reactions even though most future applications like EVs demand much higher energy densities than current ones. Exploring the exceptional reaction mechanism and related electrode materials can be critical for pushing current battery technology to a next level. Here, we introduce an exceptional reaction with a Co(OH)(2) material which exhibits an initial charge capacity of 1112 mAh g(-1), about twice its theoretical value based on known conventional conversion reaction, and retains its first cycle capacity after 30 cycles. The combined results of synchrotronmore » X-ray diffraction and X-ray absorption spectroscopy indicate that nanosized Co metal particles and LiOH are generated by conversion reaction at high voltages, and CoxHy, Li2O, and LiH are subsequently formed by hydride reaction between Co metal, LiOH, and other lithium species at low voltages, resulting in a anomalously high capacity beyond the theoretical capacity of Co(OH)(2). This is further corroborated by AIMD simulations, localized STEM, and XPS. These findings will provide not only further understanding of exceptional lithium storage of recent nanostructured materials but also valuable guidance to develop advanced electrode materials with high energy density for next-generation batteries.« less

Stochastic model for the 3D microstructure of pristine and cyclically aged cathodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Kuchler, Klaus; Westhoff, Daniel; Feinauer, Julian; Mitsch, Tim; Manke, Ingo; Schmidt, Volker

2018-04-01

It is well-known that the microstructure of electrodes in lithium-ion batteries strongly affects their performance. Vice versa, the microstructure can exhibit strong changes during the usage of the battery due to aging effects. For a better understanding of these effects, mathematical analysis and modeling has turned out to be of great help. In particular, stochastic 3D microstructure models have proven to be a powerful and very flexible tool to generate various kinds of particle-based structures. Recently, such models have been proposed for the microstructure of anodes in lithium-ion energy and power cells. In the present paper, we describe a stochastic modeling approach for the 3D microstructure of cathodes in a lithium-ion energy cell, which differs significantly from the one observed in anodes. The model for the cathode data enhances the ideas of the anode models, which have been developed so far. It is calibrated using 3D tomographic image data from pristine as well as two aged cathodes. A validation based on morphological image characteristics shows that the model is able to realistically describe both, the microstructure of pristine and aged cathodes. Thus, we conclude that the model is suitable to generate virtual, but realistic microstructures of lithium-ion cathodes.

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode-Electrolyte Interface in Lithium-Ion Batteries.

PubMed

Gao, Han; Maglia, Filippo; Lamp, Peter; Amine, Khalil; Chen, Zonghai

2017-12-27

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in lithium-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a "corrosion inhibitor film" that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot be mitigated. Effect of two exemplary electrolyte additives, lithium difluoro(oxalato)borate (LiDFOB) and 3-hexylthiophene (3HT), on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next-generation high-energy-density lithium-ion chemistries.

Large-mode-area single-mode-output Neodymium-doped silicate glass all-solid photonic crystal fiber

PubMed Central

Li, Wentao; Chen, Danping; Qinling, Zhou; Hu, Lili

2015-01-01

We have demonstrated a 45 μm core diameter Neodymium-doped all-solid silicate glass photonic crystal fiber laser with a single mode laser output. The structure parameters and modes information of the fiber are both demonstrated by theoretical calculations using Finite Difference Time Domain (FDTD) method and experimental measurements. Maximum 0.8 W output power limited by launched pump power has been generated in 1064 nm with laser beam quality factor M2 1.18. PMID:26205850

Pressure-induced coordination changes in alkali-germanate melts - An in situ spectroscopic investigation

NASA Technical Reports Server (NTRS)

Farber, Danial L.; Williams, Quentin

1992-01-01

The structure of liquid Na2Ge2O5-H2O, a silicate melt analog, has been studied with Raman spectroscopy to pressures of 2.2 gigapascals. Upon compression, a peak near more than 240 wavenumbers associated with octahedral GeO6 groups grows relative to a peak near 500 wavenumbers associated with tetrahedral GeO4 groups. This change corresponds to an increase in octahedral germanium in the liquid from near 0 percent at ambient pressures to more than 50 percent at a pressure of 2.2 gigapascals. Silicate liquids pausibly undergo similar coordination changes at depth in the earth. Such structural changes may generate decreases in the fusion slopes of silicates at high pressures as well as neutrally buoyant magmas within the transition zone of the earth's mantle.

Electrochemical and thermodynamic studies of the electrode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Bang, Hyun Joo

A series of graphite samples were tested for their electrochemical performance as anode material for lithium ion cells. Specially treated natural graphite samples showed good reversible capacities and relatively small irreversible capacity losses. The good performance of these samples can be explained by the low surface area associated with the rounded edges and absence of exfoliation due to the presence of the rhombohedral phase and defects in the grain boundaries. Graphitized cokes showed larger irreversible capacity losses while mesophase carbons showed lower reversible capacity. The treated natural graphite samples, especially LBG25 were found to be high performance, low cost anode materials for the lithium ion cells. The electrochemical and thermal behaviors of the spinels---LiMn 2O4, LiCo1/6Mn11/6O4, LiFe 1/6Mn11/6O4, and LiNi1/6Mn11/6 O4 were studied using electrochemical and thermochemical techniques. The electrochemical techniques included cyclic voltammetry, charge/discharge cycling of 2016 coin cells and diffusion coefficient measurements using Galvanostatic Intermittent Titration Technique. Better capacity retention(GITT) was observed for the substituted spinels (0.11% loss/cycle for LiCo1/6Mn 11/6O4; 0.3% loss/cycle for LiFe1/6Mn11/6 O4; and 0.2% loss/cycle for LiNi1/6Mn11/6 O4) than for the lithium manganese dioxide spinel (1.6% loss/cycle for first 10 cycles, 0.9% loss/cycle for 33 cycles) during 33 cycles. The Differential Scanning Calorimetry (DSC) results showed that the cobalt substituted spinel has better thermal stability than the lithium manganese oxide and other substituted spinels. The thermal profile of LiMn2O4 and LiAl0.17 Mn1.83O3.97S0.03 was measured in an isothermal micro-calorimeter. The heat contributions are discussed in terms of reversible and irreversible heat generation, in combination with the entropy change directly obtained by the dE/dT measurements and the over-potential measurements. The endothermic and exothermic heat profiles observed during the charge and discharge processes are related to the Li insertion/extraction reaction in the spinel host structure for both materials. The reversible heat generation due to the lithium insertion/extraction reaction in the host electrode is estimated on the basis of the cell entropy change. The heat generation calculated from DeltaS and the open circuit potential results is consistent with the heat profile (exothermic/endothermic) generated during the charge/discharge process and with the magnitude of the heat generation from the experimental results obtained from the IMC at a slow charge/discharge rate. The irreversible heat generation dependence on the current rate is discussed at different discharge rates.

Origin of silicic crust by rifting and bimodal plume volcanism in the Afar Depression

NASA Astrophysics Data System (ADS)

Ghatak, A.; Basu, A. R.; Ebinger, C. J.

2010-12-01

The youngest mantle plume province worldwide occurs at the seismically and volcanically active East African - Red Sea - Gulf of Aden (Afar) triple junction, where one or more upwellings has impinged the thick cratonic lithosphere since ~45 Ma. A spectacular example of magmatism in the Afar depression is seen in the present to < 2 Ma old bimodal fissural mafic and peralkaline silicic eruptions in the ~60 km-long Dabbahu-Manda Hararo (DMH) Rift. In this study we report major, trace elements, and Nd-Sr-Pb isotopes in recent basaltic and silicic rocks originating from the center of the DMH rift segment, exposed along the rift axis and flanks of this segment. The rare earth element (REE) patterns of the silicic rocks and basalts are different in two significant ways: (1) the silicic rocks show a prominent positive Ce-anomaly that is extremely rare in volcanic rocks; and (2) this positive Ce-anomaly is accompanied by a strong negative Eu-anomaly. These anomalies are absent in the basaltic rocks. The positive Ce-anomaly is probably due to interaction in a magma chamber, similar in composition to the basalts, with deep saline aquifer or brines that typically show positive Ce-anomaly. The REE patterns of the two lava groups are interpreted to be due to fractional crystallization of plagioclase in a magma chamber similar in REE composition as the basalts that erupted in the DMH segments. We interpret the silicic rocks to be residues after ~20% fractional crystallization of plagioclase in the DMH basalts. The Nd-Pb isotopic composition of the basalts and rhyolites of the DMH are similar to the Ethiopian plume as defined by the ~30 Ma old Ethiopian flood basalts. Based on their high 3He/4He ratios (R/RA ~30) and Nd-Sr-Pb isotopic data, the source of the Ethiopian plume is generally believed to be in the lower mantle. Therefore, the similarity of the Nd-Pb and Pb-Pb isotopic variations between the Ethiopian plume and the DMH lavas indicates that these lavas were sourced from the lower mantle, and this source zone showed little variation over the past 30 Ma. Some of the silicic lavas fall distinctly outside the plume field toward more radiogenic 87Sr/86Sr at relatively restricted Nd and Pb isotopic compositions. This excursion in Sr-isotopic ratios of the silicic lavas, in concert with their positive Ce-anomaly, is interpreted to be due to mixing of the Afar plume derived basaltic magma with fluids from saline aquifers. We conclude that the bimodal lavas are consanguineous, the silicic lavas being generated by fractional crystallization of plagioclase in a lower mantle plume-derived basaltic magma-chamber, caused by the interaction with saline aquifers. The generation of bimodal volcanism from parental primitive basalts without any contribution from pre-existing continental crust in Dabbahu may explain other similar intraplate magmatism including early Archean-Hadean continental crust formation prior to onset of arc-volcanism.

Silicate Weathering and Pervasive Authigenic Carbonate Precipitation Coupled to Methanogenesis in the Krishna-Godavari Basin, Offshore India

NASA Astrophysics Data System (ADS)

Solomon, E. A.; Spivack, A. J.; Kastner, M.; Torres, M. E.

2014-12-01

The cycling of methane in marine sediments has been actively studied for the past several decades, but less attention has been paid to the cycling of CO2 produced in methanogenic sediments. The National Gas Hydrate Program Expedition 01 cored 10 sites with the Joides Resolution drillship in the Krishna-Godavari basin, located on the southeastern margin of India. A comprehensive suite of pore water solute concentrations and isotope ratios were analyzed to investigate the distribution and concentration of gas hydrate along the margin, in situ diagenetic and metabolic reactions, fluid migration and flow pathways, and fluid and gas sources. This represents one of the most comprehensive pore water geochemical datasets collected at a continental margin to date, and provides the necessary tracers to better understand the processes and sinks controlling CO2 in margin sediments. Our results show that the CO2 produced through net microbial methanogenesis is effectively neutralized through silicate weathering throughout the sediment column drilled at each site (~100-300 m), buffering the pH of the sedimentary pore water and generating excess alkalinity through the same reaction sequence as continental silicate weathering. Most of the excess alkalinity produced through silicate weathering in the Krishna-Godavari basin is sequestered in Ca- and Fe-carbonates as a result of ubiquitous calcium release from weathering detrital silicates and Fe-reduction within the methanogenic sediments. Formation of secondary hydrous silicates (e.g. smectite) related to incongruent primary silicate dissolution acts as a significant sink for pore water Mg, K, Li, Rb, and B. The consumption of methane through anaerobic oxidation of methane, sequestration of methane in gas hydrate, and sequestration of dissolved inorganic carbon in authigenic carbonates keeps methanogenesis as a thermodynamically feasible catabolic pathway. Our results combined with previous indications of silicate weathering in anoxic sediments in the Sea of Okhotsk, suggest that silicate weathering coupled to microbial methanogenesis should be occurring in continental margins worldwide, providing a net sink of atmospheric CO2 over geologic timescales.

Lithium ion beam divergence on SABRE extraction ion diode experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanson, D.L.; Cuneo, M.E.; Johnson, D.J.

Intense lithium beams are of particular interest for light ion inertial confinement fusion applications because lithium ions can be accelerated at high voltage in a single charge state (Li{sup +}) with a high mass-to-charge ratio and appropriate range for efficient focusing and heating of a hohlraum ICF target. Scaling to ion power densities adequate to drive high gain pellet implosions (600 TW at 30 MeV) will require a large number of beams transported, temporally bunched, and focused onto a target, with the necessary target standoff to ensure survival of the driver modules. For efficient long distance transport and focusing tomore » a small pellet, lithium beam divergence must be reduced to about 12 mrad or less (depending on the transport scheme). To support the eventual development of a light ion driver module for ICF applications, the authors are currently working to improve the composition, uniformity, and divergence of lithium ion beams produced by both passive LiF and active laser-generated lithium ion sources on extraction applied-B ion diodes on the SABRE accelerator (1 TW, 5 MV, 250 kA). While lithium beam divergence accounting and control are an essential goal of these experiments, divergence measurements for lithium beams present some unique problems not encountered to the same degree in divergence measurements on proton sources. To avoid these difficulties, the authors have developed a large aperture ion imaging diagnostic for time-resolved lithium divergence measurements. The authors will report on the operation of this lithium beam divergence diagnostic and on results of time-resolved divergence measurements in progress for passive LiF ion sources and laser-produced active lithium sources operated in diode configurations designed to control divergence growth. Comparisons will also be made with time-integrated divergence results obtained with small entrance aperture ultracompact pinhole cameras.« less

Self-Action of Second Harmonic Generation and Longitudinal Temperature Gradient in Nonlinear-Optical Crystals

NASA Astrophysics Data System (ADS)

Baranov, A. I.; Konyashkin, A. V.; Ryabushkin, O. A.

2015-09-01

Model of second harmonic generation with thermal self-action was developed. Second harmonic generation temperature phase matching curves were measured and calculated for periodically polled lithium niobate crystal. Both experimental and calculated data show asymmetrical shift of temperature tuning curves with pump power.

Wnt and lithium: a common destiny in the therapy of nervous system pathologies?

PubMed

Meffre, Delphine; Grenier, Julien; Bernard, Sophie; Courtin, Françoise; Dudev, Todor; Shackleford, Ghjuvan'Ghjacumu; Jafarian-Tehrani, Mehrnaz; Massaad, Charbel

2014-04-01

Wnt signaling is required for neurogenesis, the fate of neural progenitors, the formation of neuronal circuits during development, neuron positioning and polarization, axon and dendrite development and finally for synaptogenesis. This signaling pathway is also implicated in the generation and differentiation of glial cells. In this review, we describe the mechanisms of action of Wnt signaling pathways and their implication in the development and correct functioning of the nervous system. We also illustrate how a dysregulated Wnt pathway could lead to psychiatric, neurodegenerative and demyelinating pathologies. Lithium, used for the treatment of bipolar disease, inhibits GSK3β, a central enzyme of the Wnt/β-catenin pathway. Thus, lithium could, to some extent, mimic Wnt pathway. We highlight the possible dialogue between lithium therapy and modulation of Wnt pathway in the treatment of the diseases of the nervous system.

Li+-Permeable Film on Lithium Anode for Lithium Sulfur Battery.

PubMed

Yang, Yan-Bo; Liu, Yun-Xia; Song, Zhiping; Zhou, Yun-Hong; Zhan, Hui

2017-11-08

Lithium-sulfur (Li-S) battery is an important candidate for next-generation energy storage. However, the reaction between polysulfide and lithium (Li) anode brings poor cycling stability, low Coulombic efficiency, and Li corrosion. Herein, we report a Li protection technology. Li metal was treated in crown ether containing electrolyte, and thus, treated Li was further used as the anode in Li-S cell. Due to the coordination between Li + and crown ether, a Li + -permeable film can be formed on Li, and the film is proved to be able to block the detrimental reaction between Li anode and polysulfide. By using the Li anode pretreated in 2 wt % B15C5-containing electrolyte, Li-S cell exhibits significantly improved cycling stability, such as∼900 mAh g -1 after 100 cycles, and high Coulombic efficiency of>93%. In addition, such effect is also notable when high S loading condition is applied.

Lithium nickel cobalt manganese oxide synthesized using alkali chloride flux: morphology and performance as a cathode material for lithium ion batteries.

PubMed

Kim, Yongseon

2012-05-01

Li(Ni(0.8)Co(0.1)Mn(0.1))O(2) (NCM811) was synthesized using alkali chlorides as a flux and the performance as a cathode material for lithium ion batteries was examined. Primary particles of the powder were segregated and grown separately in the presence of liquid state fluxes, which induced each particle to be composed of one primary particle with well-developed facet planes, not the shape of agglomerates as appears with commercial NCMs. The new NCM showed far less gas emission during high temperature storage at charged states, and higher volumetric capacity thanks to its high bulk density. The material is expected to provide optimal performances for pouch type lithium ion batteries, which require high volumetric capacity and are vulnerable to deformation caused by gas generation from the electrode materials.

A Compact Self-Driven Liquid Lithium Loop for Industrial Neutron Generation

NASA Astrophysics Data System (ADS)

Stemmley, Steven; Szott, Matt; Kalathiparambil, Kishor; Ahn, Chisung; Jurczyk, Brian; Ruzic, David

2017-10-01

A compact, closed liquid lithium loop has been developed at the University of Illinois to test and utilize the Li-7(d,n) reaction. The liquid metal loop is housed in a stainless steel trench module with embedded heating and cooling. The system was designed to handle large heat and particle fluxes for use in neutron generators as well as fusion devices, solely operating via thermo-electric MHD. The objectives of this project are two-fold, 1) produce a high energy, MeV-level, neutron source and 2) provide a self-healing, low Z, low recycling plasma facing component. The flowing volume will keep a fresh, clean, lithium surface allowing Li-7(d,n) reactions to occur as well as deuterium adsorption in the fluid, increasing the overall neutron output. Expected yields of this system are 107 n/s for 13.5 MeV neutrons and 108 n/s for 2.45 MeV neutrons. Previous work has shown that using a tapered trench design prevents dry out and allows for an increase in velocity of the fluid at the particle strike point. For heat fluxes on the order of 10's MW/m2, COMSOL models have shown that high enough velocities ( 70 cm/s) are attainable to prevent significant lithium evaporation. Future work will be aimed at addressing wettability issues of lithium in the trenches, experimentally determine the velocities required to prevent dry out, and determine the neutron output of the system. The preliminary results and discussion will be presented. DOE SBIR project DE-SC0013861.

Fluid Sources at the Panasqueira Tungsten-Vein Deposit

NASA Astrophysics Data System (ADS)

Lecumberri-Sanchez, P.; Heinrich, C. A.; Wälle, M.; Codeço, M.; Weis, P.; Pinto, F.; Vieira, R.

2017-12-01

Panasqueira is a world-class tungsten-vein deposit. Several paragenetic stages have been proposed (Polya et al., 2000) including two pre-ore stages (crack-seal quartz-seam, and muscovite selvages) and four ore stages (main oxide-silicate stage, main sulfide stage, pyrrhotite alteration stage, and late carbonate stage). In this study, compositions of the mineralizing fluids at Panasqueira have been determined by a combination of detailed petrography, microthermometric measurements and LA-ICPMS analyses. We have characterized the fluids related to several mineralizing stages and determined the information they provide about the fluid sources in this system. Three fluid generations recorded in pseudosecondary to secondary fluid inclusions have been identified at Panasqueira. The first fluid generation identified consists of CO2-bearing fluid inclusions with homogenization temperatures ranging between 260 and 320 °C and salinities between 5 and 8 eq wt % NaCl. Petrographic constraints indicate that this first generation (1) is paragenetically related to the main oxide-silicate stage. Two lower-temperature CO2-absent fluid generations (2a and 2b) have been identified and are represented by secondary fluid inclusions postdating the main oxide-silicate stage. This stage was likely trapped under high pressures and lithostatic conditions (Jacques and Pascal, 2017). Generation (2a) consists of high-salinity (20-30 eq wt % NaCl) fluids with homogenization temperatures ranging between 180°C and 250°C. Generation (2b) consists of low-salinity (<2 wt %) low homogenization temperature (100-150°C) fluid inclusions. Conclusive petrographic evidence of the relationship between these two late-stage fluid generations and specific late mineral stages are scarce. However, fluid compositions suggests that generation (2a) is related to the main sulfide stage and generation (2b) is related to the late carbonate stage. The PTX evolution of fluids at Panasqueira indicate a transition from magmatic dominated fluids to a likely influx of non-magmatic fluids at least in the latest stages of mineralization (main sulfide stage and late carbonate stage) which is in good agreement with recent results from isotopic studies (Codeço et al., 2017).

Continuing clozapine treatment with lithium in schizophrenic patients with neutropenia or leukopenia: brief review of literature with case reports

PubMed Central

Aydin, Memduha; Ilhan, Bilge Cetin; Calisir, Saliha; Yildirim, Seda; Eren, Ibrahim

2016-01-01

Objective: Clozapine is a second-generation antipsychotic used for treatment-resistant schizophrenia. Despite its effectiveness, clozapine is largely underused due to serious side effects such as leukopenia or neutropenia. We aimed to review whether to continue, discontinue or rechallenge clozapine treatment after such haematological side effects. Methods: We reviewed and summarized the literature on the use of clozapine, how to deal with its side effects, and suitable options in case of any haematological problems. Then, we described several cases successfully treated with clozapine and lithium after development of neutropenia or leukopenia Results: We present three patients with treatment-resistant schizophrenia. While they had demonstrated poor response to multiple antipsychotic trials, clozapine was started. Clozapine induced neutropenia; or leukopenia developed in some cases that was successfully reversed after lithium onset. Increased serious side effects related with coprescription of lithium and clozapine were not observed. Conclusion: Lithium increases neutrophil and total white blood cell count as a side effect that may be useful in patients who develop neutropenia or leukopenia while being treated with clozapine. PMID:26913176

Porous Carbon Paper as Interlayer to Stabilize the Lithium Anode for Lithium-Sulfur Battery.

PubMed

Kong, Ling-Long; Zhang, Ze; Zhang, Ye-Zheng; Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

2016-11-23

The lithium-sulfur (Li-S) battery is expected to be the high-energy battery system for the next generation. Nevertheless, the degradation of lithium anode in Li-S battery is the crucial obstacle for practical application. In this work, a porous carbon paper obtained from corn stalks via simple treating procedures is used as interlayer to stabilize the surface morphology of Li anode in the environment of Li-S battery. A smooth surface morphology of Li is obtained during cycling by introducing the porous carbon paper into Li-S battery. Meanwhile, the electrochemical performance of sulfur cathode is partially enhanced by alleviating the loss of soluble intermediates (polysulfides) into the electrolyte, as well as the side reaction of polysulfides with metallic lithium. The Li-S battery assembled with the interlayer exhibits a large capacity and excellent capacity retention. Therefore, the porous carbon paper as interlayer plays a bifunctional role in stabilizing the Li anode and enhancing the electrochemical performance of the sulfur cathode for constructing a stable Li-S battery.

Continuing clozapine treatment with lithium in schizophrenic patients with neutropenia or leukopenia: brief review of literature with case reports.

PubMed

Aydin, Memduha; Ilhan, Bilge Cetin; Calisir, Saliha; Yildirim, Seda; Eren, Ibrahim

2016-02-01

Clozapine is a second-generation antipsychotic used for treatment-resistant schizophrenia. Despite its effectiveness, clozapine is largely underused due to serious side effects such as leukopenia or neutropenia. We aimed to review whether to continue, discontinue or rechallenge clozapine treatment after such haematological side effects. We reviewed and summarized the literature on the use of clozapine, how to deal with its side effects, and suitable options in case of any haematological problems. Then, we described several cases successfully treated with clozapine and lithium after development of neutropenia or leukopenia. We present three patients with treatment-resistant schizophrenia. While they had demonstrated poor response to multiple antipsychotic trials, clozapine was started. Clozapine induced neutropenia; or leukopenia developed in some cases that was successfully reversed after lithium onset. Increased serious side effects related with coprescription of lithium and clozapine were not observed. Lithium increases neutrophil and total white blood cell count as a side effect that may be useful in patients who develop neutropenia or leukopenia while being treated with clozapine.

Distinct lithium-induced gene expression effects in lymphoblastoid cell lines from patients with bipolar disorder.

PubMed

Fries, Gabriel R; Colpo, Gabriela D; Monroy-Jaramillo, Nancy; Zhao, Junfei; Zhao, Zhongming; Arnold, Jodi G; Bowden, Charles L; Walss-Bass, Consuelo

2017-11-01

Lithium is the most commonly prescribed medication for the treatment of bipolar disorder (BD), yet the mechanisms underlying its beneficial effects are still unclear. We aimed to compare the effects of lithium treatment in lymphoblastoid cell lines (LCLs) from BD patients and controls. LCLs were generated from sixty-two BD patients (based on DSM-IV) and seventeen healthy controls matched for age, sex, and ethnicity. Patients were recruited from outpatient clinics from February 2012 to October 2014. LCLs were treated with 1mM lithium for 7 days followed by microarray gene expression assay and validation by real-time quantitative PCR. Baseline differences between groups, as well as differences between vehicle- and lithium-treated cells within each group were analyzed. The biological significance of differentially expressed genes was examined by pathway enrichment analysis. No significant differences in baseline gene expression (adjusted p-value < 0.05) were detected between groups. Lithium treatment of LCLs from controls did not lead to any significant differences. However, lithium altered the expression of 236 genes in LCLs from patients; those genes were enriched for signaling pathways related to apoptosis. Among those genes, the alterations in the expression of PIK3CG, SERP1 and UPP1 were validated by real-time PCR. A significant correlation was also found between circadian functioning and CEBPG and FGF2 expression levels. In summary, our results suggest that lithium treatment induces expression changes in genes associated with the apoptosis pathway in BD LCLs. The more pronounced effects of lithium in patients compared to controls suggest a disease-specific effect of this drug. Copyright © 2017 Elsevier B.V. and ECNP. All rights reserved.

Analysis of heat generation of lithium ion rechargeable batteries used in implantable battery systems for driving undulation pump ventricular assist device.

PubMed

Okamoto, Eiji; Nakamura, Masatoshi; Akasaka, Yuhta; Inoue, Yusuke; Abe, Yusuke; Chinzei, Tsuneo; Saito, Itsuro; Isoyama, Takashi; Mochizuki, Shuichi; Imachi, Kou; Mitamura, Yoshinori

2007-07-01

We have developed internal battery systems for driving an undulation pump ventricular assist device using two kinds of lithium ion rechargeable batteries. The lithium ion rechargeable batteries have high energy density, long life, and no memory effect; however, rise in temperature of the lithium ion rechargeable battery is a critical issue. Evaluation of temperature rise by means of numerical estimation is required to develop an internal battery system. Temperature of the lithium ion rechargeable batteries is determined by ohmic loss due to internal resistance, chemical loss due to chemical reaction, and heat release. Measurement results of internal resistance (R(cell)) at an ambient temperature of 37 degrees C were 0.1 Omega in the lithium ion (Li-ion) battery and 0.03 Omega in the lithium polymer (Li-po) battery. Entropy change (DeltaS) of each battery, which leads to chemical loss, was -1.6 to -61.1 J/(mol.K) in the Li-ion battery and -9.6 to -67.5 J/(mol.K) in the Li-po battery depending on state of charge (SOC). Temperature of each lithium ion rechargeable battery under a discharge current of 1 A was estimated by finite element method heat transfer analysis at an ambient temperature of 37 degrees C configuring with measured R(cell) and measured DeltaS in each SOC. Results of estimation of time-course change in the surface temperature of each battery coincided with results of measurement results, and the success of the estimation will greatly contribute to the development of an internal battery system using lithium ion rechargeable batteries.

Polyethylene oxide film coating enhances lithium cycling efficiency of an anode-free lithium-metal battery.

PubMed

Assegie, Addisu Alemayehu; Cheng, Ju-Hsiang; Kuo, Li-Ming; Su, Wei-Nien; Hwang, Bing-Joe

2018-03-29

The practical implementation of an anode-free lithium-metal battery with promising high capacity is hampered by dendrite formation and low coulombic efficiency. Most notably, these challenges stem from non-uniform lithium plating and unstable SEI layer formation on the bare copper electrode. Herein, we revealed the homogeneous deposition of lithium and effective suppression of dendrite formation using a copper electrode coated with a polyethylene oxide (PEO) film in an electrolyte comprising 1 M LiTFSI, DME/DOL (1/1, v/v) and 2 wt% LiNO3. More importantly, the PEO film coating promoted the formation of a thin and robust SEI layer film by hosting lithium and regulating the inevitable reaction of lithium with the electrolyte. The modified electrode exhibited stable cycling of lithium with an average coulombic efficiency of ∼100% over 200 cycles and low voltage hysteresis (∼30 mV) at a current density of 0.5 mA cm-2. Moreover, we tested the anode-free battery experimentally by integrating it with an LiFePO4 cathode into a full-cell configuration (Cu@PEO/LiFePO4). The new cell demonstrated stable cycling with an average coulombic efficiency of 98.6% and capacity retention of 30% in the 200th cycle at a rate of 0.2C. These impressive enhancements in cycle life and capacity retention result from the synergy of the PEO film coating, high electrode-electrolyte interface compatibility, stable polar oligomer formation from the reduction of 1,3-dioxolane and the generation of SEI-stabilizing nitrite and nitride upon lithium nitrate reduction. Our result opens up a new route to realize anode-free batteries by modifying the copper anode with PEO to achieve ever more demanding yet safe interfacial chemistry and control of dendrite formation.

The effects of particle swarm optimization algorithm on volume ignition gain of Proton-Lithium (7) pellets

NASA Astrophysics Data System (ADS)

Livari, As. Ali; Malekynia, B.; Livari, Ak. A.; Khoda-Bakhsh, R.

2017-11-01

When it was found out that the ignition of nuclear fusion hinges upon input energy laser, the efforts in order to make giant lasers began, and energy gains of DT fuel were obtained. But due to the neutrons generation and emitted radioactivity from DT reaction, gains of fuels like Proton-Lithium (7) were also adverted. Therefore, making larger and powerful lasers was followed. Here, using new versions of particle swarm optimization algorithm, it will be shown that available maximum gain of Proton-Lithium (7) is reached only at energies about 1014 J, and not only the highest input energy is not helpful but the efficiency is also decreased.

Summary Report on the Navy Emergency Escape Breathing Device

DTIC Science & Technology

1983-08-08

recirculated cas. The device produces pure oxygen (02) and uses a venturi to recirculate unused and expired gases through the purifier. A rubber...passing the recirculated air through a lithium hydroxide (LiOH) scrubber . The scrubber reduces the CO. level by forming either lithium bicarbonate (LiSCO...transparent visor and an elastromeric neck seal; a chlorate candle-based 02 generator; an air purification filter or scrubberl and a venturi arrangement to

Lithium perchlorate-nitromethane-promoted alkylation of anilines with arylmethanols.

PubMed

Zhou, Jun; Mao, Hai-Feng; Wang, Lu; Zou, Jian-Ping; Zhang, Wei

2011-11-01

A new application of lithium perchlorate-nitromethane (LPNM) for the formation of aromatic C-N and C-C bonds is introduced. LPNM-promoted reactions of anilines with diarylmethanols selectively generate N-alkylated anilines or mono and double Friedel-Crafts alkylation products under different conditions by changing the reaction time, reaction temperature, and the ratio of the reactants. This method does not require the use of transition metal catalysts to prepare alkylated aniline derivatives.

An Energy Dense-AI-NaBH4-PEMFC Based Power Generator for Unmanned Undersea Vehicles

DTIC Science & Technology

2016-03-01

1]. Although different types of batteries involving lithium , e.g., primary (Li-SOCb) and rechargeable (Li- ion , Li-polymer) batteries , potentially...development of innovative beyond battery -only technological capabilities would be necessary. The main objective of the proposed work is to develop an...increasing the endurance of UUVs. Lithium is commonly used in battery technology because it is the lightest metal , so higher energy densities are possible

Distributed Storage Inverter and Legacy Generator Integration Plus Renewables Solution for Microgrids

DTIC Science & Technology

2015-07-01

Reactive kVAR Kilo Watts kW Lithium Ion Li Ion Lithium-Titanate Oxide nLTO Natural gas NG Performance Objectives PO Photovoltaic PV Power ...cloud covered) periods. The demonstration features a large (relative to the overall system power requirements) photovoltaic solar array, whose inverter...microgrid with less expensive power storage instead of large scale energy storage and that the renewable energy with small-scale power storage can

Acousto-ultrasonic evaluation of ceramic matrix composite materials

NASA Technical Reports Server (NTRS)

Dosreis, Henrique L. M.

1991-01-01

Acousto-ultrasonic nondestructive evaluation of ceramic composite specimens with a lithium-alumino-silicate glass matrix reinforced with unidirectional silicon carbide (NICALON) fibers was conducted to evaluate their reserve of strength. Ceramic composite specimens with different amount of damage were prepared by four-point cyclic fatigue loading of the specimens at 500 C for a different number of cycles. The reserve of strength of the specimens was measured as the maximum bending stress recorded during four-pointed bending test with the load monotonically increased until failure occurs. It was observed that the reserve of strength did not correlate with the number of fatigue cycles. However, it was also observed that higher values of the stress wave factor measurements correspond to higher values of the reserve of strength test data. Therefore, these results show that the acousto-ultrasonic approach has the potential of being used to monitor damage and to estimate the reserve of strength of ceramic composites.

Glass-fiber-based neutron detectors for high- and low-flux environments

NASA Astrophysics Data System (ADS)

Bliss, Mary; Brodzinski, Ronald L.; Craig, Richard A.; Geelhood, Bruce D.; Knopf, Michael A.; Miley, Harry S.; Perkins, Richard W.; Reeder, Paul L.; Sunberg, Debra S.; Warner, Ray A.; Wogman, Ned A.

1995-09-01

Pacific Northwest Laboratory (PNL) has fabricated cerium-activated lithium silicate scintillating fibers via a hot-downdraw process. These fibers typically have a operational transmission length (e(superscript -1) length) of greater than 2 meters. This permits the fabrication of devices which were not possible to consider. Scintillating fibers permit conformable devices, large-area devices, and extremely small devices; in addition, as the thermal-neutron sensitive elements in a fast neutron detection system, scintillating fibers can be dispersed within moderator, improving neutron economy, over that possible with commercially available (superscript 3)He or BF(subscript 3) proportional counters. These fibers can be used for national-security applications, in medical applications, in the nuclear-power industry, and for personnel protection at experimental facilities. Data are presented for devices based on single fibers and devices made up of ribbons containing many fibers under high-and low-flux conditions.

Nondestructive monitoring damage in composites using scanning laser acoustic microscopy

NASA Technical Reports Server (NTRS)

Wey, A. C.; Kessler, L. W.; Dos Reis, H. L. M.

1992-01-01

Several Nicalon fiber reinforced LAS (lithium alumino-silicate) glass matrix composites were tested to study the relation between the residual strength and the different amounts of damage. The samples were fatigued by four-point cyclic loading at a 5 Hz rate at 500 C for a different number of cycles. 10 MHz scanning laser acoustic microscope (SLAM) images were taken to monitor damage on the samples. Our SLAM results indicate that there were defects already existing throughout the sample before fatigue, and the resultant damage pattern from fatigue could be related to the initial defect distribution in the sample. Finally, the fatigued samples were fractured and the residual strength data could not be explained by the cyclic fatigue alone. Rather, the damage patterns evident in the SLAM images were needed to explain the scatter in the data. The results show that SLAM is useful in nondestructively monitoring damage and estimating residual strength of fatigued ceramic composites.

Electrochemical performance of carbon-coated lithium manganese silicate for asymmetric hybrid supercapacitors

NASA Astrophysics Data System (ADS)

Karthikeyan, K.; Aravindan, V.; Lee, S. B.; Jang, I. C.; Lim, H. H.; Park, G. J.; Yoshio, M.; Lee, Y. S.

Nanoscale carbon-coated Li 2MnSiO 4 powder is prepared using a conventional solid-state method and can be used as the negative electrode in a Li 2MnSiO 4/activated carbon (AC) hybrid supercapacitor. Carbon-coated Li 2MnSiO 4 material presents a well-developed orthorhombic crystal structure with a P mn2 1 space group, although there is a small impurity of MnO. The maximum specific capacitance of the Li 2MnSiO 4/AC hybrid supercapacitor is 43.2 F g -1 at 1 mA cm -2 current density. The cell delivers a specific energy as high as 54 Wh kg -1 at a specific power of 150 W kg -1 and also exhibits an excellent cycle performance with more than 99% columbic efficiency and the maintenance of 85% of its initial capacitance after 1000 cycles.

Dependence of the critical cooling rate for lithium-silicate glass on nucleating agents

NASA Technical Reports Server (NTRS)

Huang, W.; Ray, C. S.; Day, D. E.

1986-01-01

The critical cooling rate, Rc, for glass formation of a glass containing 40 mol pct Li2O and 60 mol pct SiO2, doped with small amounts of Pt, Au, P2O5, and TiO2 nucleating agents, has been measured. Rc increases with increasing Pt and Au additions, but Pt has a larger effect than Au. Additions of P2O5 tend to decrease Rc, whereas TiO2 has practically no effect on Rc. The devitrified glass nucleated with Pt contains only crystalline Li2O-SiO2, but all the other devitrified glasses, including the undoped glass, contain both Li2O-SiO2 and Li2O-2SiO2. Analysis shows that Rc increases as the concentration of the Li2O-SiO2 phase in the devitrified glass increases.

Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component

NASA Technical Reports Server (NTRS)

Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

2009-01-01

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium diboride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Variations in Gas and Water Pulses at an Arctic Seep: Fluid Sources and Methane Transport

NASA Astrophysics Data System (ADS)

Hong, W.-L.; Torres, M. E.; Portnov, A.; Waage, M.; Haley, B.; Lepland, A.

2018-05-01

Methane fluxes into the oceans are largely dependent on the methane phase as it migrates upward through the sediments. Here we document decoupled methane transport by gaseous and aqueous phases in Storfjordrenna (offshore Svalbard) and propose a three-stage evolution model for active seepage in the region where gas hydrates are present in the shallow subsurface. In a preactive seepage stage, solute diffusion is the primary transport mechanism for methane in the dissolved phase. Fluids containing dissolved methane have high 87Sr/86Sr ratios due to silicate weathering in the microbial methanogenesis zone. During the active seepage stage, migration of gaseous methane results in near-seafloor gas hydrate formation and vigorous seafloor gas discharge with a thermogenic fingerprint. In the postactive seepage stage, the high concentration of dissolved lithium points to the contribution of a deeper-sourced aqueous fluid, which we postulate advects upward following cessation of gas discharge.

Modeling of steady-state convective cooling of cylindrical Li-ion cells

NASA Astrophysics Data System (ADS)

Shah, K.; Drake, S. J.; Wetz, D. A.; Ostanek, J. K.; Miller, S. P.; Heinzel, J. M.; Jain, A.

2014-07-01

While Lithium-ion batteries have the potential to serve as an excellent means of energy storage, they suffer from several operational safety concerns. Temperature excursion beyond a specified limit for a Lithium-ion battery triggers a sequence of decomposition and release, which can preclude thermal runaway events and catastrophic failure. To optimize liquid or air-based convective cooling approaches, it is important to accurately model the thermal response of Lithium-ion cells to convective cooling, particularly in high-rate discharge applications where significant heat generation is expected. This paper presents closed-form analytical solutions for the steady-state temperature profile in a convectively cooled cylindrical Lithium-ion cell. These models account for the strongly anisotropic thermal conductivity of cylindrical Lithium-ion batteries due to the spirally wound electrode assembly. Model results are in excellent agreement with experimentally measured temperature rise in a thermal test cell. Results indicate that improvements in radial thermal conductivity and axial convective heat transfer coefficient may result in significant peak temperature reduction. Battery sizing optimization using the analytical model is discussed, indicating the dependence of thermal performance of the cell on its size and aspect ratio. Results presented in this paper may aid in accurate thermal design and thermal management of Lithium-ion batteries.

Investigation of gold and bimetallic gold/silver nanoparticles in soda-lime-silicate glasses formed by means of excimer laser irradiation

NASA Astrophysics Data System (ADS)

Heinz, M.; Dubiel, M.; Meinertz, J.; Ihlemann, J.; Hoell, A.

2017-02-01

In this study, plasmonic Au and Au/Ag nanostructures in soda-lime-silicate glasses have been generated by means of ArF-excimer laser irradiation (193 nm) below the ablation threshold of the glass. For this purpose pure and silver/sodium ion-exchanged float glasses have been coated by gold and then irradiated by the laser. The formation of Au and Au/Ag nanoparticles could be verified by the surface plasmon resonances between 420 and 620 nm, which were obtained by optical spectroscopy. Both, pure Au and Ag particles as well as bimetallic Au/Ag nanoparticles, could be observed by means of small angle X-ray scattering experiments. These results demonstrate that such procedures enable the spaceselected generation of plasmonic nanostructures in glass surfaces by excimer laser irradiation.

Influence of commercial and residual sorbents and silicates as additives on the stabilisation/solidification of organic and inorganic industrial waste.

PubMed

Coz, A; Andrés, A; Soriano, S; Viguri, J R; Ruiz, M C; Irabien, J A

2009-05-30

An environmental problem of the foundry activities is the management of industrial waste generated in different processes. The foundry sludge from gas wet cleaning treatment that contains organic and inorganic compounds and a high content of water is an interesting example. Due to their characteristics, they can be managed using different stabilisation/solidification (S/S) technologies prior to land disposal. The purpose of this work is to study S/S formulations in order to improve the control of the mobility of the pollutants and the ecotoxicity of the samples. Different mixtures of cement or lime as binders and additives (foundry sand, silica fume, sodium silicate, silicic acid, activated carbon and black carbon) have been used in order to reduce the mobility of the chemical and ecotoxicological regulated parameters and to compare the results for commercial and residual additives. The best results have been obtained with sorbents (activated carbon and black carbon) or sodium silicate. The results of the foundry sand ash as additive can conclude that it can be used as replacement in the cement products. However, silica fume in the samples with lime and siliceous resin sand as additives gives products that do not fulfil the regulated limits. Finally, some linear expressions between the chemical parameters and the quantity of material used in the samples have been obtained.

Rb3In(H2O)Si5O13: a novel indium silicate with a CdSO4-topological-type structure.

PubMed

Hung, Ling-I; Wang, Sue-Lein; Chen, Chia-Yi; Chang, Bor-Chen; Lii, Kwang-Hwa

2005-05-02

A novel indium silicate, Rb3In(H2O)Si5O13, has been synthesized using a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. The structure consists of five-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to four adjacent five-membered rings to form a 3D silicate framework that belongs to the CdSO4 topological type. The InO6 octahedron shares five of its corners with five different SiO4 tetrahedra to form a 3D frame-work that delimits two types of channels to accommodate the rubidium cations. The sixth corner of InO6 is coordinated H2O. The structure is related to that of the titanium silicate ETS-10, and these are the only two metal silicates that have the CdSO4-topological-type structure. In addition, the crystal of Rb3In(H2O)Si5O13 shows an intense second harmonic generation signal. Crystal data: H2Rb3InSi5O14, monoclinic, space group Cc (No. 9), a = 9.0697(5) A, b = 11.5456(6) A, c = 13.9266(8) A, beta = 102.300(1) degrees, V = 1424.8(1) A3, and Z = 4.

Desulfurization of fuel gases in fluidized bed gasification and hot fuel gas cleanup systems

DOEpatents

Steinberg, M.; Farber, G.; Pruzansky, J.; Yoo, H.J.; McGauley, P.

1983-08-26

A problem with the commercialization of fluidized bed gasification is that vast amounts of spent sorbent are generated if the sorbent is used on a once-through basis, especially if high sulfur coals are burned. The requirements of a sorbent for regenerative service in the FBG process are: (1) it must be capable of reducing the sulfur containing gas concentration of the FBG flue gas to within acceptable environmental standards; (2) it must not lose its reactivity on cyclic sulfidation and regeneration; (3) it must be capable of regeneration with elimination of substantially all of its sulfur content; (4) it must have good attrition resistance; and, (5) its cost must not be prohibitive. It has now been discovered that calcium silicate pellets, e.g., Portland cement type III pellets meet the criteria aforesaid. Calcium silicate removes COS and H/sub 2/S according to the reactions given to produce calcium sulfide silicate. The sulfur containing product can be regenerated using CO/sub 2/ as the regenerant. The sulfur dioxide can be conveniently reduced to sulfur with hydrogen or carbon for market or storage. The basic reactions in the process of this invention are the reactions with calcium silicate given in the patent. A convenient and inexpensive source of calcium silicate is Portland cement. Portland cement is a readily available, widely used construction meterial.

Bandwidth tunable THz wave generation in large-area periodically poled lithium niobate.

PubMed

Zhang, Caihong; Avetisyan, Yuri; Glosser, Andreas; Kawayama, Iwao; Murakami, Hironaru; Tonouchi, Masayoshi

2012-04-09

A new scheme of optical rectification (OR) of femtosecond laser pulses in a periodically poled lithium niobate (PPLN) crystal, which generates high energy and bandwidth tunable multicycle THz pulses, is proposed and demonstrated. We show that the number of the oscillation cycles of the THz electric field and therefore bandwidth of generated THz spectrum can easily and smoothly be tuned from a few tens of GHz to a few THz by changing the pump optical spot size on PPLN crystal. The minimal bandwidth is 17 GHz that is smallest ever of reported in scheme of THz generation by OR at room temperature. Similar to the case of Cherenkov-type OR in single-domain LiNbO₃, the spectrum of THz generation extends from 0.1 THz to 3 THz when laser beam is focused to a size close to half-period of PPLN structure. The energy spectral density of narrowband THz generation is almost independent of the bandwidth and is typically 220 nJ/THz for ~1 W pump power at 1 kHz repetition rate.

Tip-induced nanoreactor for silicate

NASA Astrophysics Data System (ADS)

Gao, Ming; Ma, Liran; Liang, Yong; Gao, Yuan; Luo, Jianbin

2015-09-01

Nanoscale scientific issues have attracted an increasing amount of research interest due to their specific size-effect and novel structure-property. From macro to nano, materials present some unique chemical reactivity that bulk materials do not own. Here we introduce a facile method to generate silicate with nanoscale control based on the establishment of a confined space between a meso/nanoscale tungsten tip and a smooth silica/silicon substrate. During the process, local water-like droplets deposition can be obviously observed in the confinement between the Si/SiO2 surfaces and the KOH-modified tungsten tip. By the combination of in-situ optical microscopy and Raman spectroscopy, we were able to take a deep insight of both the product composition and the underlying mechanism of such phenomena. It was indicated that such nanoreactor for silicate could be quite efficient as a result of the local capillarity and electric field effect, with implications at both nano and meso scales.

Tip-induced nanoreactor for silicate.

PubMed

Gao, Ming; Ma, Liran; Liang, Yong; Gao, Yuan; Luo, Jianbin

2015-09-14

Nanoscale scientific issues have attracted an increasing amount of research interest due to their specific size-effect and novel structure-property. From macro to nano, materials present some unique chemical reactivity that bulk materials do not own. Here we introduce a facile method to generate silicate with nanoscale control based on the establishment of a confined space between a meso/nanoscale tungsten tip and a smooth silica/silicon substrate. During the process, local water-like droplets deposition can be obviously observed in the confinement between the Si/SiO2 surfaces and the KOH-modified tungsten tip. By the combination of in-situ optical microscopy and Raman spectroscopy, we were able to take a deep insight of both the product composition and the underlying mechanism of such phenomena. It was indicated that such nanoreactor for silicate could be quite efficient as a result of the local capillarity and electric field effect, with implications at both nano and meso scales.

Tip-induced nanoreactor for silicate

PubMed Central

Gao, Ming; Ma, Liran; Liang, Yong; Gao, Yuan; Luo, Jianbin

2015-01-01

Nanoscale scientific issues have attracted an increasing amount of research interest due to their specific size-effect and novel structure-property. From macro to nano, materials present some unique chemical reactivity that bulk materials do not own. Here we introduce a facile method to generate silicate with nanoscale control based on the establishment of a confined space between a meso/nanoscale tungsten tip and a smooth silica/silicon substrate. During the process, local water-like droplets deposition can be obviously observed in the confinement between the Si/SiO2 surfaces and the KOH-modified tungsten tip. By the combination of in-situ optical microscopy and Raman spectroscopy, we were able to take a deep insight of both the product composition and the underlying mechanism of such phenomena. It was indicated that such nanoreactor for silicate could be quite efficient as a result of the local capillarity and electric field effect, with implications at both nano and meso scales. PMID:26364882

Experimental modeling of the interaction of subducted carbonates and sulfur with mantle silicates

NASA Astrophysics Data System (ADS)

Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Zdrokov, E. V.; Sobolev, N. V.

2016-09-01

Experimental studies in the system Fe,Ni-olivine-carbonate-S ( P = 6.3 GPa, T = 1050-1550°C, t = 40-60 h) aimed at modeling of the interaction of subducted carbonates and sulfur with rocks of the silicate mantle and at investigation of the likely mechanism of the formation of mantle sulfides were performed. It is shown that an association of olivine + orthopyroxene + magnesite + pyrite coexisting with a sulfur melt/fluid with dissolved Fe, Ni, and O is formed at T ≤ 1250°C. An association of low-Fe olivine, orthopyroxene, and magnesite and two immiscible melts of the carbonate and S-Fe-Ni-O compositions are formed at T ≥ 1350°C. It is shown that the reduced S-bearing fluids may transform silicates and carbonates, extract metals from the solid-phase matrix, and provide conditions for generation of sulfide melts.

Improvement of the model for surface process of tritium release from lithium oxide

NASA Astrophysics Data System (ADS)

Yamaki, Daiju; Iwamoto, Akira; Jitsukawa, Shiro

2000-12-01

Among the various tritium transport processes in lithium ceramics, the importance and the detailed mechanism of surface reactions remain to be elucidated. The dynamic adsorption and desorption model for tritium desorption from lithium ceramics, especially Li 2O was constructed. From the experimental results, it was considered that both H 2 and H 2O are dissociatively adsorbed on Li 2O and generate OH - on the surface. In the first model developed in 1994, it was assumed that either the dissociative adsorption of H 2 or H 2O on Li 2O generates two OH - on the surface. However, recent calculation results show that the generation of one OH - and one H - is more stable than that of two OH -s by the dissociative adsorption of H 2. Therefore, assumption of H 2 adsorption and desorption in the first model is improved and the tritium release behavior from Li 2O surface is evaluated again by using the improved model. The tritium residence time on the Li 2O surface is calculated using the improved model, and the results are compared with the experimental results. The calculation results using the improved model agree well with the experimental results than those using the first model.

Temperature-dependent electrochemical heat generation in a commercial lithium-ion battery

NASA Astrophysics Data System (ADS)

Bandhauer, Todd M.; Garimella, Srinivas; Fuller, Thomas F.

2014-02-01

Lithium-ion batteries suffer from inherent thermal limitations (i.e., capacity fade and thermal runaway); thus, it is critical to understand heat generation experienced in the batteries under normal operation. In the current study, reversible and irreversible electrochemical heat generation rates were measured experimentally on a small commercially available C/LiFePO4 lithium-ion battery designed for high-rate applications. The battery was tested over a wide range of temperatures (10-60 °C) and discharge and charge rates (∼C/4-5C) to elucidate their effects. Two samples were tested in a specially designed wind tunnel to maintain constant battery surface temperature within a maximum variation of ±0.88 °C. A data normalization technique was employed to account for the observed capacity fade, which was largest at the highest rates. The heat rate was shown to increase with both increasing rate and decreasing temperature, and the reversible heat rate was shown to be significant even at the highest rate and temperature (7.4% at 5C and 55 °C). Results from cycling the battery using a dynamic power profile also showed that constant-current data predict the dynamic performance data well. In addition, the reversible heat rate in the dynamic simulation was shown to be significant, especially for charge-depleting HEV applications.

Electrochemistry of Sulfur Dioxide in Nonaqueous Solutions. Part I.

DTIC Science & Technology

1981-05-18

carried out as part of a program to investigate safety hazards in nonaqueous ambient temperature lithium batteries. Comparison and discussion of...behavior of nonaqueous solutions of sulfur dioxide has been generated by the use of these systems in high energy density lithium batteries. During the past... hexafluorophosphate ) 6 at -0.13V and +0.63V (vs. AgCl coated Ag wire), which were assigned to the oxidation of S02- and 62042-. Fouchard observed that the

Hydrometallurgical process for recovery of cobalt from waste cathodic active material generated during manufacturing of lithium ion batteries

NASA Astrophysics Data System (ADS)

Swain, Basudev; Jeong, Jinki; Lee, Jae-chun; Lee, Gae-Ho; Sohn, Jeong-Soo

The paper presents a new leaching-solvent extraction hydrometallurgical process for the recovery of a pure and marketable form of cobalt sulfate solution from waste cathodic active material generated during manufacturing of lithium ion batteries (LIBs). Leaching of the waste was carried out as a function of the leachant H 2SO 4 concentration, temperature, pulp density and reductant H 2O 2 concentration. The 93% of cobalt and 94% of lithium were leached at suitable optimum conditions of pulp density: 100 g L -1, 2 M H 2SO 4, 5 vol.% of H 2O 2, with a leaching time 30 min and a temperature 75 °C. In subsequent the solvent extraction study, 85.42% of the cobalt was recovered using 1.5 M Cyanex 272 as an extractant at an O/A ratio of 1.6 from the leach liquor at pH 5.00. The rest of the cobalt was totally recovered from the raffinate using 0.5 M of Cyanex 272 and an O/A ratio of 1, and a feed pH of 5.35. Then the co-extracted lithium was scrubbed from the cobalt-loaded organic using 0.1 M Na 2CO 3. Finally, the cobalt sulfate solution with a purity 99.99% was obtained from the cobalt-loaded organic by stripping with H 2SO 4.

Oxidative decomposition of propylene carbonate in lithium ion batteries: a DFT study.

PubMed

Leggesse, Ermias Girma; Lin, Rao Tung; Teng, Tsung-Fan; Chen, Chi-Liang; Jiang, Jyh-Chiang

2013-08-22

This paper reports an in-depth mechanistic study on the oxidative decomposition of propylene carbonate in the presence of lithium salts (LiClO4, LiBF4, LiPF6, and LiAsF6) with the aid of density functional theory calculations at the B3LYP/6-311++G(d,p) level of theory. The solvent effect is accounted for by using the implicit solvation model with density method. Moreover, the rate constants for the decompositions of propylene carbonate have been investigated by using transition-state theory. The shortening of the original carbonyl C-O bond and a lengthening of the adjacent ethereal C-O bonds of propylene carbonate, which occurs as a result of oxidation, leads to the formation of acetone radical and CO2 as a primary oxidative decomposition product. The termination of the primary radical generates polycarbonate, acetone, diketone, 2-(ethan-1-ylium-1-yl)-4-methyl-1,3-dioxolan-4-ylium, and CO2. The thermodynamic and kinetic data show that the major oxidative decomposition products of propylene carbonate are independent of the type of lithium salt. However, the decomposition rate constants of propylene carbonate are highly affected by the lithium salt type. On the basis of the rate constant calculations using transition-state theory, the order of gas volume generation is: [PC-ClO4](-) > [PC-BF4](-) > [PC-AsF6](-) > [PC-PF6](-).

Mood stabilizers in pregnancy and child developmental outcomes: A systematic review.

PubMed

Haskey, Carolyn; Galbally, Megan

2017-11-01

Research suggests that maintaining treatment during pregnancy for women with bipolar affective disorder reduces the risk of relapse. However, one of the key questions for women and clinicians during pregnancy is whether there are implications of exposure to mood stabilizers for longer term child development. Despite these concerns, there are few recent systematic reviews comparing the impact on child developmental outcomes for individual mood-stabilizing agents to inform clinical decisions. To examine the strengths and limitations of the existing data on child developmental outcomes following prenatal exposure to mood stabilizers and to explore whether there are any differences between agents for detrimental effects on child development. Using the Preferred Reporting Items for Systematic Reviews and Meta-Analyses guidelines, a rigorous systematic search was carried out of four electronic databases from their respective years of inception to September 2016 to identify studies which examined the effects of mood stabilizers including sodium valproate, carbamazepine, lamotrigine, lithium and second-generation antipsychotics on child developmental outcomes. We identified 15 studies for critical review. Of these, 10 examined antiepileptic drugs, 2 studied lithium and 3 studied second-generation antipsychotics. The most consistent finding was a dose-response relationship for valproate with higher doses associated with poorer global cognitive abilities compared to other antiepileptic drugs. The limited data available for lithium found no adverse neurodevelopmental outcomes. The limited second-generation antipsychotic studies included a report of a transient early neurodevelopmental delay which resolved by 12 months of age. This review found higher neurodevelopmental risk with valproate. While the existing data on lithium and second-generation antipsychotics are reassuring, these data are both limited and lower quality, indicating that further research is required. The information from this review is relevant for patients and clinicians to influence choice of mood-stabilizing agent in childbearing women. This must be balanced against the known risks associated with untreated bipolar affective disorder.

Ultrasmall Zeolite L Crystals Prepared from Highly-Interdispersed Alkali-Silicate Precursors.

PubMed

Li, Rui; Linares, Noemi; Sutjianto, James G; Chawla, Aseem; Garcia Martinez, Javier; Rimer, Jeffrey D

2018-06-19

The preparation of nanosized zeolites is critical for applications where mass transport limitations within microporous networks hinder their performance. Oftentimes the ability to generate ultrasmall zeolite crystals is dependent upon the use of expensive organics with limited commercial relevance. Here, we report the generation of zeolite L crystals with uniform sizes less than 30 nm using a facile, organic-free method. Time-resolved analysis of precursor assembly and evolution during nonclassical crystallization highlights key differences among silicon sources. Our findings reveal that a homogenous dispersion of potassium ions throughout silicate precursors is critical to enhancing the rate of nucleation and facilitating the formation of ultrasmall crystals. Intimate contact between the inorganic structure-directing agent and silica leads to the formation of a metastable nonporous phase, identified as KAlSi2O6, which undergoes an intercrystalline transformation to zeolite L. The presence of highly-interdispersed alkali-silicate precursors is seemingly integral to a reduced zeolite induction time and may facilitate the development of ultrasmall crystals. Given the general difficulty of achieving nanosized crystals in zeolite synthesis, it is likely that using well-dispersed precursors does not have the same effect on all framework types; however, in select cases it may provide an alternative strategy for optimizing zeolite synthesis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Progress in Synthesis and Application of Low-Dimensional Silicon Based Anode Material for Lithium Ion Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yuandong; Liu, Kewei; Zhu, Yu

Silicon is regarded as the next generation anode material for LIBs with its ultra-high theoretical capacity and abundance. Nevertheless, the severe capacity degradation resulting from the huge volume change and accumulative solid-electrolyte interphase (SEI) formation hinders the silicon based anode material for further practical applications. Hence, a variety of methods have been applied to enhance electrochemical performances in terms of the electrochemical stability and rate performance of the silicon anodes such as designing nanostructured Si, combining with carbonaceous material, exploring multifunctional polymer binders, and developing artificial SEI layers. Silicon anodes with low-dimensional structures (0D, 1D, and 2D), compared with bulkymore » silicon anodes, are strongly believed to have several advanced characteristics including larger surface area, fast electron transfer, and shortened lithium diffusion pathway as well as better accommodation with volume changes, which leads to improved electrochemical behaviors. Finally, in this review, recent progress of silicon anode synthesis methodologies generating low-dimensional structures for lithium ion batteries (LIBs) applications is listed and discussed.« less

A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

PubMed

Xia, Yan; Wang, Xiuli; Xia, Xinhui; Xu, Ruochen; Zhang, Shengzhao; Wu, Jianbo; Liang, Yanfei; Gu, Changdong; Tu, Jiangping

2017-10-26

Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g -1 at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Progress in Synthesis and Application of Low-Dimensional Silicon Based Anode Material for Lithium Ion Battery

DOE PAGES

Sun, Yuandong; Liu, Kewei; Zhu, Yu

2017-07-31

Silicon is regarded as the next generation anode material for LIBs with its ultra-high theoretical capacity and abundance. Nevertheless, the severe capacity degradation resulting from the huge volume change and accumulative solid-electrolyte interphase (SEI) formation hinders the silicon based anode material for further practical applications. Hence, a variety of methods have been applied to enhance electrochemical performances in terms of the electrochemical stability and rate performance of the silicon anodes such as designing nanostructured Si, combining with carbonaceous material, exploring multifunctional polymer binders, and developing artificial SEI layers. Silicon anodes with low-dimensional structures (0D, 1D, and 2D), compared with bulkymore » silicon anodes, are strongly believed to have several advanced characteristics including larger surface area, fast electron transfer, and shortened lithium diffusion pathway as well as better accommodation with volume changes, which leads to improved electrochemical behaviors. Finally, in this review, recent progress of silicon anode synthesis methodologies generating low-dimensional structures for lithium ion batteries (LIBs) applications is listed and discussed.« less

One-Pot Synthesis of Lithium-Rich Cathode Material with Hierarchical Morphology.

PubMed

Luo, Kun; Roberts, Matthew R; Hao, Rong; Guerrini, Niccoló; Liberti, Emanuela; Allen, Christopher S; Kirkland, Angus I; Bruce, Peter G

2016-12-14

Lithium-rich transition metal oxides, Li 1+x TM 1-x O 2 (TM, transition metal), have attracted much attention as potential candidate cathode materials for next generation lithium ion batteries because their high theoretical capacity. Here we present the synthesis of Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 using a facile one-pot resorcinol-formaldehyde method. Structural characterization indicates that the material adopts a hierarchical porous morphology consisting of uniformly distributed small pores and disordered large pore structures. The material exhibits excellent electrochemical cycling stability and a good retention of capacity at high rates. The material has been shown to be both advantageous in terms of gravimetric and volumetric capacities over state of the art commercial cathode materials.

Variation of lithium isotope geochemistry during basalt weathering and secondary mineral transformations in Hawaii

NASA Astrophysics Data System (ADS)

Ryu, Jong-Sik; Vigier, Nathalie; Lee, Sin-Woo; Lee, Kwang-Sik; Chadwick, Oliver A.

2014-11-01

Lithium isotopes are a potential tracer of silicate weathering but the relationship between lithium isotope compositions and weathering state still need to be established with precision. Here, we report Li concentrations and Li isotope compositions of soils developed along a 4 million year humid-environment chronosequence in the Hawaiian Islands. Li concentrations are variable with depth and age, ranging from 0.24 to 21.3 ppm, and significant Li depletions (up to 92%) relative to parent basalts are systematically enhanced towards the surface. Our calculations show that the relative contribution from atmospheric deposits to the Li soil budget remains small, with a maximum contribution from dust Li of 20% at the oldest site. This is explained by the capacity of the weathering products to retain, within the profiles, the Li coming from basalt alteration, and allows us to explore more specifically the role of alteration processes on soil Li isotope signatures. The δ7Li values display a large range between -2.5‰ and +13.9‰. The youngest soils (0.3 ka) display the same δ7Li value as fresh basalt, regardless of depth, despite ∼30% Li loss by leaching, indicating that there is little Li isotope fractionation during the incipient stage of weathering. δ7Li values for the older soils (⩾20 ka) vary non-linearly as a function of time and can be explained by progressive mineral transformations starting with the synthesis of metastable short-range order (nano-crystalline) minerals and followed by their transformation into relatively inert secondary minerals. Results highlight significant Li isotope fractionation during secondary mineral formation and in particular during Li uptake by kaolinite. Finally, we suggest that the non-monotonous evolution of the regolith δ7Li value over the last 4 Ma is consistent with climatic variations, where congruent release of Li isotopes occurs during warmer periods.

Lithium isotope constraints on crust-mantle interactions and surface processes on Mars

NASA Astrophysics Data System (ADS)

Magna, Tomáš; Day, James M. D.; Mezger, Klaus; Fehr, Manuela A.; Dohmen, Ralf; Aoudjehane, Hasnaa Chennaoui; Agee, Carl B.

2015-08-01

Lithium abundances and isotope compositions are reported for a suite of martian meteorites that span the range of petrological and geochemical types recognized to date for Mars. Samples include twenty-one bulk-rock enriched, intermediate and depleted shergottites, six nakhlites, two chassignites, the orthopyroxenite Allan Hills (ALH) 84001 and the polymict breccia Northwest Africa (NWA) 7034. Shergottites unaffected by terrestrial weathering exhibit a range in δ7Li from 2.1 to 6.2‰, similar to that reported for pristine terrestrial peridotites and unaltered mid-ocean ridge and ocean island basalts. Two chassignites have δ7Li values (4.0‰) intermediate to the shergottite range, and combined, these meteorites provide the most robust current constraints on δ7Li of the martian mantle. The polymict breccia NWA 7034 has the lowest δ7Li (-0.2‰) of all terrestrially unaltered martian meteorites measured to date and may represent an isotopically light surface end-member. The new data for NWA 7034 imply that martian crustal surface materials had both a lighter Li isotope composition and elevated Li abundance compared with their associated mantle. These findings are supported by Li data for olivine-phyric shergotitte NWA 1068, a black glass phase isolated from the Tissint meteorite fall, and some nakhlites, which all show evidence for assimilation of a low-δ7Li crustal component. The range in δ7Li for nakhlites (1.8 to 5.2‰), and co-variations with chlorine abundance, suggests crustal contamination by Cl-rich brines. The differences in Li isotope composition and abundance between the martian mantle and estimated crust are not as large as the fractionations observed for terrestrial continental crust and mantle, suggesting a difference in the styles of alteration and weathering between water-dominated processes on Earth versus possibly Cl-S-rich brines on Mars. Using high-MgO shergottites (>15 wt.% MgO) it is possible to estimate the δ7Li of Bulk Silicate Mars (BSM) to be 4.2 ± 0.9‰ (2σ). This value is at the higher end of estimates for the Bulk Silicate Earth (BSE; 3.5 ± 1.0‰, 2σ), but overlaps within uncertainty.

Advanced sensible heat solar receiver for space power

NASA Technical Reports Server (NTRS)

Bennett, Timothy J.; Lacy, Dovie E.

1988-01-01

NASA Lewis, through in-house efforts, has begun a study to generate a conceptual design of a sensible heat solar receiver and to determine the feasibility of such a system for space power applications. The sensible heat solar receiver generated in this study uses pure lithium as the thermal storage medium and was designed for a 7 kWe Brayton (PCS) operating at 1100 K. The receiver consists of two stages interconnected via temperature sensing variable conductance sodium heat pipes. The lithium is contained within a niobium vessel and the outer shell of the receiver is constructed of third generation rigid, fibrous ceramic insulation material. Reradiation losses are controlled with niobium and aluminum shields. By nature of design, the sensible heat receiver generated in this study is comparable in both size and mass to a latent heat system of similar thermal capacitance. The heat receiver design and thermal analysis was conducted through the combined use of PATRAN, SINDA, TRASYS, and NASTRAN software packages.

Advanced sensible heat solar receiver for space power

NASA Technical Reports Server (NTRS)

Bennett, Timothy J.; Lacy, Dovie E.

1988-01-01

NASA Lewis, through in-house efforts, has begun a study to generate a conceptual design of a sensible heat solar receiver and to determine the feasibility of such a system for space power applications. The sensible heat solar receiver generated in this study uses pure lithium as the thermal storage medium and was designed for a 7 kWe Brayton (PCS) operating at 1100 K. The receiver consists of two stages interconnected via temperature sensing variable conductance sodium heat pipes. The lithium is contained within a niobium vessel and the outer shell of the receiver is constructed of third generation rigid, fibrous ceramic insulation material. Reradiation losses are controlled with niobium and aluminum shields. By nature of design, the sensible heat receiver generated in this study is comparable in both size and mass to a latent heat system of similar thermal capacitance. The heat receiver design and thermal analysis were conducted through the combined use of PATRAN, SINDA, TRASYS, and NASTRAN software packages.

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung

2008-01-01

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

Effect of entropy change of lithium intercalation in cathodes and anodes on Li-ion battery thermal management

NASA Astrophysics Data System (ADS)

Viswanathan, Vilayanur V.; Choi, Daiwon; Wang, Donghai; Xu, Wu; Towne, Silas; Williford, Ralph E.; Zhang, Ji-Guang; Liu, Jun; Yang, Zhenguo

The entropy changes (Δ S) in various cathode and anode materials, as well as in complete Li-ion batteries, were measured using an electrochemical thermodynamic measurement system (ETMS). LiCoO 2 has a much larger entropy change than electrodes based on LiNi xCo yMn zO 2 and LiFePO 4, while lithium titanate based anodes have lower entropy change compared to graphite anodes. The reversible heat generation rate was found to be a significant portion of the total heat generation rate. The appropriate combinations of cathode and anode were investigated to minimize reversible heat generation rate across the 0-100% state of charge (SOC) range. In addition to screening for battery electrode materials with low reversible heat, the techniques described in this paper can be a useful engineering tool for battery thermal management in stationary and transportation applications.

Agile multicasting based on cascaded χ(2) nonlinearities in a step-chirped periodically poled lithium niobate.

PubMed

Ahlawat, Meenu; Bostani, Ameneh; Tehranchi, Amirhossein; Kashyap, Raman

2013-08-01

We experimentally demonstrate the possibility of agile multicasting for wavelength division multiplexing (WDM) networks, of a single-channel to two and seven channels over the C band, also extendable to S and L bands. This is based on cascaded χ(2) nonlinear mixing processes, namely, second-harmonic generation (SHG)-sum-frequency generation (SFG) and difference-frequency generation (DFG) in a 20-mm-long step-chirped periodically poled lithium niobate crystal, specially designed and fabricated for a 28-nm-wide SH-SF bandwidth centered at around 1.55 μm. The multiple idlers are simultaneously tuned by detuning the pump wavelengths within the broad SH-SF bandwidth. By selectively tuning the pump wavelengths over less than 10 and 6 nm, respectively, multicasting into two and seven idlers is successfully achieved across ~70 WDM channels within the 50 GHz International Telecommunication Union grid spacing.

Experimental constraints on mantle metasomatism caused by silicate and carbonate melts

NASA Astrophysics Data System (ADS)

Gervasoni, Fernanda; Klemme, Stephan; Rohrbach, Arno; Grützner, Tobias; Berndt, Jasper

2017-06-01

Metasomatic processes are responsible for many of the heterogeneities found in the upper mantle. To better understand the metasomatism in the lithospheric mantle and to illustrate the differences between metasomatism caused by hydrous silicate and carbonate-rich melts, we performed various interaction experiments: (1) Reactions between hydrous eclogite-derived melts and peridotite at 2.2-2.5 GPa and 900-1000 °C reproduce the metasomatism in the mantle wedge above subduction zones. (2) Reactions between carbonate-rich melts and peridotite at 2.5 GPa and 1050-1000 °C, and at 6 GPa and 1200-1250 °C simulate metasomatism of carbonatite and ultramafic silicate-carbonate melts in different regions of cratonic lithosphere. Our experimental results show that partial melting of hydrous eclogite produces hydrous Si- and Al-rich melts that react with peridotite and form bi-mineralic assemblages of Al-rich orthopyroxene and Mg-rich amphibole. We also found that carbonate-rich melts with different compositions react with peridotite and form new metasomatic wehrlitic mineral assemblages. Metasomatic reactions caused by Ca-rich carbonatite melt consume the primary peridotite and produce large amounts of metasomatic clinopyroxene; on the other hand, metasomatism caused by ultramafic silicate-carbonate melts produces less clinopyroxene. Furthermore, our experiments show that ultramafic silicate-carbonate melts react strongly with peridotite and cause crystallization of large amounts of metasomatic Fe-Ti oxides. The reactions of metasomatic melts with peridotite also change the melt composition. For instance, if the carbonatite melt is not entirely consumed during the metasomatic reactions, its melt composition may change dramatically, generating an alkali-rich carbonated silicate melt that is similar in composition to type I kimberlites.

Residual stresses and phase transformations in Ytterbium silicate environmental barrier coatings

NASA Astrophysics Data System (ADS)

Stolzenburg, Fabian

Due to their high melting temperature, low density, and good thermomechanical stability, silicon-based ceramics (SiC, Si3N4) are some of the most promising materials systems for high temperature structural applications in gas turbine engines. However, their silica surface layer reacts with water vapor contained in combustion environments. The resulting hydroxide layer volatilizes, leading to component recession. Environmental barrier coatings (EBCs) have been developed to shield the substrate from degradation. Next generation coatings for silicon-based ceramics based on ytterbium silicates have shown a promising combination of very low and good thermomechanical properties. The focus of this thesis is threefold: In the first part, phase transformations in plasma sprayed ytterbium silicates were investigated. Plasma sprayed materials are known to contain large amounts of amorphous material. Phase changes during the conversion from amorphous to crystalline materials were investigated as they have been known to lead to failure in many coatings. The second part of this work focused on measuring residual stresses in multilayer EBCs using synchrotron X-ray diffraction (XRD). Strains were resolved spatially, with probe sizes as small as 20 um. Stresses were calculated using mechanical properties of ytterbium silicates, determined with in-situ loading and heating experiments. In-situ and ex-situ heating experiments allowed for the study of changes in stress states that occur in these EBC materials during heating and cooling cycles. Lastly, the interaction of ytterbium silicates with low-melting environmental calcium-magnesium-aluminosilicate (CMAS) glasses was studied. Synchrotron XRD was used to study the influence of CMAS on the stress state in the coating, X-ray computed tomography was used to provide 3D images of coatings, and EDS and TEM analysis were used to study the interactions at the CMAS/ytterbium silicate interface in detail.

Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis.

PubMed

Reeves, Jonathan T; Malapit, Christian A; Buono, Frederic G; Sidhu, Kanwar P; Marsini, Maurice A; Sader, C Avery; Fandrick, Keith R; Busacca, Carl A; Senanayake, Chris H

2015-07-29

An electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides, by a transnitrilation with dimethylmalononitrile (DMMN) was developed. DMMN is a commercially available, bench-stable solid. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates. The transnitrilation of aryllithium species generated by directed ortho-lithiation enabled a net C-H cyanation. The intermediacy of a Thorpe-type imine adduct in the reaction was supported by isolation of the corresponding ketone from the quenched reaction. Computational studies supported the energetic favorability of retro-Thorpe fragmentation of the imine adduct.

Cascading second-order nonlinear processes in a lithium niobate-on-insulator microdisk.

PubMed

Liu, Shijie; Zheng, Yuanlin; Chen, Xianfeng

2017-09-15

Whispering-gallery-mode (WGM) microcavities are very important in both fundamental science and practical applications, among which on-chip second-order nonlinear microresonators play an important role in integrated photonic functionalities. Here we demonstrate resonant second-harmonic generation (SHG) and cascaded third-harmonic generation (THG) in a lithium niobate-on-insulator (LNOI) microdisk resonator. Efficient SHG in the visible range was obtained with only several mW input powers at telecom wavelengths. THG was also observed through a cascading process, which reveals simultaneous phase matching and strong mode coupling in the resonator. Cascading of second-order nonlinear processes gives rise to an effectively large third-order nonlinearity, which makes on-chip second-order nonlinear microresonators a promising frequency converter for integrated nonlinear photonics.

A preliminary study on the short-term efficacy of chairside computer-aided design/computer-assisted manufacturing- generated posterior lithium disilicate crowns.

PubMed

Reich, Sven; Fischer, Sören; Sobotta, Bernhard; Klapper, Horst-Uwe; Gozdowski, Stephan

2010-01-01

The purpose of this preliminary study was to evaluate the clinical performance of chairside-generated crowns over a preliminary time period of 24 months. Forty-one posterior crowns made of a machinable lithium disilicate ceramic for full-contour crowns were inserted in 34 patients using a chairside computer-aided design/computer-assisted manufacturing technique. The crowns were evaluated at baseline and after 6, 12, and 24 months according to modified United States Public Health Service criteria. After 2 years, all reexamined crowns (n = 39) were in situ; one abutment exhibited secondary caries and two abutments received root canal treatment. Within the limited observation period, the crowns revealed clinically satisfying results.

High sulfur-containing carbon polysulfide polymer as a novel cathode material for lithium-sulfur battery.

PubMed

Zhang, Yiyong; Peng, Yueying; Wang, Yunhui; Li, Jiyang; Li, He; Zeng, Jing; Wang, Jing; Hwang, Bing Joe; Zhao, Jinbao

2017-09-12

The lithium-sulfur battery, which offers a high energy density and is environmental friendly, is a promising next generation of rechargeable energy storage system. However, despite these attractive attributes, the commercialization of lithium-sulfur battery is primarily hindered by the parasitic reactions between the Li metal anode and dissolved polysulfide species from the cathode during the cycling process. Herein, we synthesize the sulfur-rich carbon polysulfide polymer and demonstrate that it is a promising cathode material for high performance lithium-sulfur battery. The electrochemical studies reveal that the carbon polysulfide polymer exhibits superb reversibility and cycle stability. This is due to that the well-designed structure of the carbon polysulfide polymer has several advantages, especially, the strong chemical interaction between sulfur and the carbon framework (C-S bonds) inhibits the shuttle effect and the π electrons of the carbon polysulfide compound enhance the transfer of electrons and Li + . Furthermore, as-prepared carbon polysulfide polymer-graphene hybrid cathode achieves outstanding cycle stability and relatively high capacity. This work highlights the potential promise of the carbon polysulfide polymer as the cathode material for high performance lithium-sulfur battery.

Detection of endogenous lithium in neuropsychiatric disorders--a model for biological transmutation.

PubMed

Kurup, Ravi Kumar; Kurup, Parameswara Achutha

2002-01-01

The human hypothalamus produces an endogenous membrane Na(+)-K(+) ATPase inhibitor, digoxin. A digoxin induced model of cellular/neuronal quantal state and perception has been described by the authors. Biological transmutation has been described in microbial systems in the quantal state. The study focuses on the plasma levels of digoxin, RBC membrane Na(+)-K(+) ATPase activity, plasma levels of magnesium and lithium in neuropsychiatric and systemic disorders. Inhibition of RBC membrane Na(+)-K(+) ATPase activity was observed in most cases along with an increase in the levels of serum digoxin and lithium and a decrease in the level of serum Mg(++). The generation of endogenous lithium would obviously occur due to biological transmutation from magnesium. Digoxin and lithium together can produce added membrane Na(+)-K(+) ATPase inhibition. The role of membrane Na(+)-K(+) ATPase inhibition in the pathogenesis of neuropsychiatric and systemic disorders is discussed. The inhibition of membrane Na(+)-K(+) ATPase can contribute to an increase in intracellular calcium and a decrease in magnesium, which can result in a defective neurotransmitter transport mechanism, mitochondrial dysfunction and apoptosis, defective golgi body function and protein processing dysfunction, immune dysfunction and oncogenesis. Copyright 2002 John Wiley & Sons, Ltd.

Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 2, chemical-mechanical degradation model

NASA Astrophysics Data System (ADS)

Purewal, Justin; Wang, John; Graetz, Jason; Soukiazian, Souren; Tataria, Harshad; Verbrugge, Mark W.

2014-12-01

Capacity fade is reported for 1.5 Ah Li-ion batteries containing a mixture of Li-Ni-Co-Mn oxide (NCM) + Li-Mn oxide spinel (LMO) as positive electrode material and a graphite negative electrode. The batteries were cycled at a wide range of temperatures (10 °C-46 °C) and discharge currents (0.5C-6.5C). The measured capacity losses were fit to a simple physics-based model which calculates lithium inventory loss from two related mechanisms: (1) mechanical degradation at the graphite anode particle surface caused by diffusion-induced stresses (DIS) and (2) chemical degradation caused by lithium loss to continued growth of the solid-electrolyte interphase (SEI). These two mechanisms are coupled because lithium is consumed through SEI formation on newly exposed crack surfaces. The growth of crack surface area is modeled as a fatigue phenomenon due to the cyclic stresses generated by repeated lithium insertion and de-insertion of graphite particles. This coupled chemical-mechanical degradation model is consistent with the observed capacity loss features for the NCM + LMO/graphite cells.

A multi scale multi-dimensional thermo electrochemical modelling of high capacity lithium-ion cells

NASA Astrophysics Data System (ADS)

Tourani, Abbas; White, Peter; Ivey, Paul

2014-06-01

Lithium iron phosphate (LFP) and lithium manganese oxide (LMO) are competitive and complementary to each other as cathode materials for lithium-ion batteries, especially for use in electric vehicles. A multi scale multi-dimensional physic-based model is proposed in this paper to study the thermal behaviour of the two lithium-ion chemistries. The model consists of two sub models, a one dimensional (1D) electrochemical sub model and a two dimensional (2D) thermo-electric sub model, which are coupled and solved concurrently. The 1D model predicts the heat generation rate (Qh) and voltage (V) of the battery cell through different load cycles. The 2D model of the battery cell accounts for temperature distribution and current distribution across the surface of the battery cell. The two cells are examined experimentally through 90 h load cycles including high/low charge/discharge rates. The experimental results are compared with the model results and they are in good agreement. The presented results in this paper verify the cells temperature behaviour at different operating conditions which will lead to the design of a cost effective thermal management system for the battery pack.

Multiphotonic Confocal Microscopy 3D imaging: Application to mantle sulfides in sub-arc environment (Avacha Volcano, Kamchatka)

NASA Astrophysics Data System (ADS)

Antoine, Bénard; Luc-Serge, Doucet; Sabine, Palle; Dmitri A., Ionov

2010-05-01

Petrogenetic relations in igneous rocks are usually studied in natural samples using classical optical microscopy and subsequent geochemical data acquisition. Multiphotonic Laser Scanning Confocal Microscopy (MLSCM) can be a powerful tool to section geological materials optically with sub-micrometric resolution and then generate a three-dimensional (3D) reconstruction (ca. 106 μm3 stack). MLSCM is used here to investigate textural relations of Monosulfide Solid Solution (MSS) with silicate phases in fresh spinel harzburgite xenoliths from the andesitic Avacha volcano (Kamchatka, Russia). The xenoliths contain MSS disseminated in olivine and orthopyroxene (opx) neoblasts as well as MSS-rich quenched magmatic opx veins [1]. First, Reflection Mode (RM) was tested on vein sulfides in resin-impregnated thick (120 μm) polished rock sections. Then we used a combination of Differential Interference Contrast (DIC) with a transmitted light detector, two photons-excited fluorescence (2PEF) and Second Harmonic Generation (SHG). Sequential imaging feature of the Leica TCS-SP2 software was applied. The excitation laser used for 2PEF was a COHERENT MIRA 900 with a 76Hz repetition rate and 800nm wavelength. Image stacks were analysed using ImageJ software [2]. The aim of the tests was to try to discriminate sulfides in silicate matrix as a tool for a better assessment of equilibrium conditions between the two phases. Preliminary results show that Fe-Ni rich MSS from vein and host rock have a strong auto-fluorescence in the Near UV-VIS domain (392-715 nm) whereas silicate matrix is only revealed through DIC. SHG is obtained only from dense nanocentrosymmetrical structures such as embedded medium (organic matter like glue and resin). The three images were recorded sequentially enabling efficient discrimination between the different components of the rock slices. RM permits reconstruction of the complete 3D structure of the rock slice. High resolution (ca. 0.2 μm along X-Y axis vs. 0.4 along Z axis) 2PEF enables analysis of 3D textural relations of tiny individual MSS globules (˜10 μm) in their various habitus. Statistical microgeometric descriptions can be derived from volumetric image data. These results may permit refinement of models concerning (re-) crystallisation kinetics and miscibility conditions of sulphur species in various media likely to act in different mantle environments: silicate melt, fluid-rich silicate melt, silicate-rich fluid. Furthermore, this study provides 3D images with improved resolution of several components (silicate phases, sulfides, silicate glass) over the full thickness (>100 μm) of rock slices which cannot be done with classical methods. Besides 3D imaging of ‘hidden' phases in mantle rocks, it opens up new possibilities for other domains in geosciences like crystallography or petrophysics. [1] Bénard & Ionov (2010) GRA, this volume [2] Abramoff, M.D., Magelhaes, P.J. & Ram, S.J. (2004) Image processing with ImageJ. Biophoton. Int., 11, 36-42

Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries.

PubMed

Kim, Ju-Myung; Park, Jang-Hoon; Lee, Chang Kee; Lee, Sang-Young

2014-04-08

As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries.

Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Kim, Ju-Myung; Park, Jang-Hoon; Lee, Chang Kee; Lee, Sang-Young

2014-04-01

As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries.

Electrode Materials, Electrolytes, and Challenges in Nonaqueous Lithium-Ion Capacitors.

PubMed

Li, Bing; Zheng, Junsheng; Zhang, Hongyou; Jin, Liming; Yang, Daijun; Lv, Hong; Shen, Chao; Shellikeri, Annadanesh; Zheng, Yiran; Gong, Ruiqi; Zheng, Jim P; Zhang, Cunman

2018-04-01

Among the various energy-storage systems, lithium-ion capacitors (LICs) are receiving intensive attention due to their high energy density, high power density, long lifetime, and good stability. As a hybrid of lithium-ion batteries and supercapacitors, LICs are composed of a battery-type electrode and a capacitor-type electrode and can potentially combine the advantages of the high energy density of batteries and the large power density of capacitors. Here, the working principle of LICs is discussed, and the recent advances in LIC electrode materials, particularly activated carbon and lithium titanate, as well as in electrolyte development are reviewed. The charge-storage mechanisms for intercalative pseudocapacitive behavior, battery behavior, and conventional pseudocapacitive behavior are classified and compared. Finally, the prospects and challenges associated with LICs are discussed. The overall aim is to provide deep insights into the LIC field for continuing research and development of second-generation energy-storage technologies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density

PubMed Central

Son, In Hyuk; Hwan Park, Jong; Kwon, Soonchul; Park, Seongyong; Rümmeli, Mark H.; Bachmatiuk, Alicja; Song, Hyun Jae; Ku, Junhwan; Choi, Jang Wook; Choi, Jae-man; Doo, Seok-Gwang; Chang, Hyuk

2015-01-01

Silicon is receiving discernable attention as an active material for next generation lithium-ion battery anodes because of its unparalleled gravimetric capacity. However, the large volume change of silicon over charge–discharge cycles weakens its competitiveness in the volumetric energy density and cycle life. Here we report direct graphene growth over silicon nanoparticles without silicon carbide formation. The graphene layers anchored onto the silicon surface accommodate the volume expansion of silicon via a sliding process between adjacent graphene layers. When paired with a commercial lithium cobalt oxide cathode, the silicon carbide-free graphene coating allows the full cell to reach volumetric energy densities of 972 and 700 Wh l−1 at first and 200th cycle, respectively, 1.8 and 1.5 times higher than those of current commercial lithium-ion batteries. This observation suggests that two-dimensional layered structure of graphene and its silicon carbide-free integration with silicon can serve as a prototype in advancing silicon anodes to commercially viable technology. PMID:26109057

Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries

PubMed Central

Kim, Ju-Myung; Park, Jang-Hoon; Lee, Chang Kee; Lee, Sang-Young

2014-01-01

As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries. PMID:24710575

A Review of State-of-the-Art Separator Materials for Advanced Lithium-Based Batteries for Future Aerospace Missions

NASA Technical Reports Server (NTRS)

Bladwin, Richard S.

2009-01-01

As NASA embarks on a renewed human presence in space, safe, human-rated, electrical energy storage and power generation technologies, which will be capable of demonstrating reliable performance in a variety of unique mission environments, will be required. To address the future performance and safety requirements for the energy storage technologies that will enhance and enable future NASA Constellation Program elements and other future aerospace missions, advanced rechargeable, lithium-ion battery technology development is being pursued with an emphasis on addressing performance technology gaps between state-of-the-art capabilities and critical future mission requirements. The material attributes and related performance of a lithium-ion cell's internal separator component are critical for achieving overall optimal performance, safety and reliability. This review provides an overview of the general types, material properties and the performance and safety characteristics of current separator materials employed in lithium-ion batteries, such as those materials that are being assessed and developed for future aerospace missions.

Determination of lithium sulphur batteries internal resistance by the pulsed method during galvanostatic cycling

NASA Astrophysics Data System (ADS)

Kolosnitsyn, V. S.; Kuzmina, E. V.; Mochalov, S. E.

2014-04-01

The pulsed method of measuring impedance is described. The cell is galvanostatically stimulated by a bipolar current signal of square shape. The cell response is registered by sampling U+[i], U-[i] with selected period Δt. The impedance spectra are calculated by direct Fourier transform. The internal resistance of the lithium sulphur cell is characteristically minimum in the calculated impedance diagrams in the frequency range of 0.035-5 Hz. It is shown that the lithium sulphur cells have maximum internal resistance at the transient between high and low voltage plateaus of charge and discharge curves. The internal resistance increases significantly during the initial stages of cycling because of the formation of passivation layers at the electrodes. It was found that the internal resistance of the lithium sulphur cell in the same charge state is governed by the way in which it is achieved. This is explained by differences in molar volumes of products generated in the sulphur electrode by electrochemical reaction during charging and discharging.

A rationally designed composite of alternating strata of Si nanoparticles and graphene: a high-performance lithium-ion battery anode.

PubMed

Sun, Fu; Huang, Kai; Qi, Xiang; Gao, Tian; Liu, Yuping; Zou, Xianghua; Wei, Xiaolin; Zhong, Jianxin

2013-09-21

We have successfully fabricated a free-standing Si-re-G (reduced graphene) alternating stratum structure composite through a repeated process of filtering liquid exfoliated graphene oxide and uniformly dispersed Si solution, followed by the reduction of graphene oxide. The as-prepared free-standing flexible alternating stratum structure composite was directly evaluated as the anode for rechargeable lithium half-cells without adding any polymer binder, conductive additives or using current collectors. The half cells based on this new alternating structure composite exhibit an unexpected capacity of 1500 mA h g(-1) after 100 cycles at 1.35 A g(-1). Our rationally proposed strategy has incorporated the long cycle life of carbon and the high lithium-storage capacity of Si into one entity using the feasible and scalable vacuum filtration technique, rendering this new protocol as a readily applicable means of addressing the practical application challenges associated with the next generation of rechargeable lithium-ion batteries.

Thermal analysis and management of lithium-titanate batteries

NASA Astrophysics Data System (ADS)

Giuliano, Michael R.; Advani, Suresh G.; Prasad, Ajay K.

2011-08-01

Battery electric vehicles and hybrid electric vehicles demand batteries that can store large amounts of energy in addition to accommodating large charge and discharge currents without compromising battery life. Lithium-titanate batteries have recently become an attractive option for this application. High current thresholds allow these cells to be charged quickly as well as supply the power needed to drive such vehicles. These large currents generate substantial amounts of waste heat due to loss mechanisms arising from the cell's internal chemistry and ohmic resistance. During normal vehicle operation, an active cooling system must be implemented to maintain a safe cell temperature and improve battery performance and life. This paper outlines a method to conduct thermal analysis of lithium-titanate cells under laboratory conditions. Thermochromic liquid crystals were implemented to instantaneously measure the entire surface temperature field of the cell. The resulting temperature measurements were used to evaluate the effectiveness of an active cooling system developed and tested in our laboratory for the thermal management of lithium-titanate cells.

Inhibiting Polysulfide Shuttle in Lithium-Sulfur Batteries through Low-Ion-Pairing Salts and a Triflamide Solvent.

PubMed

Shyamsunder, Abhinandan; Beichel, Witali; Klose, Petra; Pang, Quan; Scherer, Harald; Hoffmann, Anke; Murphy, Graham K; Krossing, Ingo; Nazar, Linda F

2017-05-22

The step-change in gravimetric energy density needed for electrochemical energy storage devices to power unmanned autonomous vehicles, electric vehicles, and enable low-cost clean grid storage is unlikely to be provided by conventional lithium ion batteries. Lithium-sulfur batteries comprising lightweight elements provide a promising alternative, but the associated polysulfide shuttle in typical ether-based electrolytes generates loss in capacity and low coulombic efficiency. The first new electrolyte based on a unique combination of a relatively hydrophobic sulfonamide solvent and a low ion-pairing salt, which inhibits the polysulfide shuttle, is presented. This system behaves as a sparingly solvating electrolyte at slightly elevated temperatures, where it sustains reversible capacities as high as 1200-1500 mAh g -1 over a wide range of current density (2C-C/5, respectively) when paired with a lithium metal anode, with a coulombic efficiency of >99.7 % in the absence of LiNO 3 additive. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Encapsulation of sulfur with thin-layered nickel-based hydroxides for long-cyclic lithium–sulfur cells

PubMed Central

Jiang, Jian; Zhu, Jianhui; Ai, Wei; Wang, Xiuli; Wang, Yanlong; Zou, Chenji; Huang, Wei; Yu, Ting

2015-01-01

Elemental sulfur cathodes for lithium/sulfur cells are still in the stage of intensive research due to their unsatisfactory capacity retention and cyclability. The undesired capacity degradation upon cycling originates from gradual diffusion of lithium polysulfides out of the cathode region. To prevent losses of certain intermediate soluble species and extend lifespan of cells, the effective encapsulation of sulfur plays a critical role. Here we report an applicable way, by using thin-layered nickel-based hydroxide as a feasible and effective encapsulation material. In addition to being a durable physical barrier, such hydroxide thin films can irreversibly react with lithium to generate protective layers that combine good ionic permeability and abundant functional polar/hydrophilic groups, leading to drastic improvements in cell behaviours (almost 100% coulombic efficiency and negligible capacity decay within total 500 cycles). Our present encapsulation strategy and understanding of hydroxide working mechanisms may advance progress on the development of lithium/sulfur cells for practical use. PMID:26470847

Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Huddleston, William; Dynys, Frederick; Sehirlioglu, Alp

2017-01-01

All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

Influence of laser pulse duration on the electrochemical performance of laser structured LiFePO4 composite electrodes

NASA Astrophysics Data System (ADS)

Mangang, M.; Seifert, H. J.; Pfleging, W.

2016-02-01

Lithium iron phosphate is a promising cathode material for lithium-ion batteries, despite its low electrical conductivity and lithium-ion diffusion kinetic. To overcome the reduced rate performance, three dimensional (3D) architectures were generated in composite cathode layers. By using ultrashort laser radiation with pulse durations in the femtosecond regime the ablation depth per pulse is three times higher compared to nanosecond laser pulses. Due to the 3D structuring, the surface area of the active material which is in direct contact with liquid electrolyte, i.e. the active surface, is increased. As a result the capacity retention and the cycle stability were significantly improved, especially for high charging/discharging currents. Furthermore, a 3D structure leads to higher currents during cyclic voltammetry. Thus, the lithium-ion diffusion kinetic in the cell was improved. In addition, using ultrashort laser pulses results in a high aspect ratio and further improvement of the cell kinetic was achieved.

Record fifth-harmonic-generation efficiency producing 211 nm, joule-level pulses using cesium lithium borate

DOE PAGES

Begishev, I. A.; Bromage, J.; Yang, S. T.; ...

2018-05-16

The fifth harmonic of a pulsed Nd:YLF laser has been realized in a cascade of nonlinear crystals with a record efficiency of 30%. Cesium lithium borate is used in a Type-I configuration for sum-frequency mixing of 1053 nm and 266 nm, producing 211-nm pulses. Flattopped beam profiles and pulse shapes optimize efficiency. Furthermore, energies of the fifth harmonic up to 335 mJ in 2.4 ns pulses were demonstrated.

Record fifth-harmonic-generation efficiency producing 211  nm, joule-level pulses using cesium lithium borate

DOE PAGES

Begishev, I. A.; Bromage, J.; Yang, S. T.; ...

2018-01-01

The fifth harmonic of a pulsed Nd:YLF laser has been realized in a cascade of nonlinear crystals with a record efficiency of 30%. Cesium lithium borate is used in a Type-I configuration for sum-frequency mixing of 1053 nm and 266 nm, producing 211-nm pulses. Flattopped beam profiles and pulse shapes optimize efficiency. Energies of the fifth harmonic up to 335 mJ in 2.4 ns pulses were demonstrated.

Record fifth-harmonic-generation efficiency producing 211 nm, joule-level pulses using cesium lithium borate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Begishev, I. A.; Bromage, J.; Yang, S. T.

The fifth harmonic of a pulsed Nd:YLF laser has been realized in a cascade of nonlinear crystals with a record efficiency of 30%. Cesium lithium borate is used in a Type-I configuration for sum-frequency mixing of 1053 nm and 266 nm, producing 211-nm pulses. Flattopped beam profiles and pulse shapes optimize efficiency. Furthermore, energies of the fifth harmonic up to 335 mJ in 2.4 ns pulses were demonstrated.

A chlorate candle/lithium hydroxide personal breathing apparatus

NASA Technical Reports Server (NTRS)

Martin, F. E.

1972-01-01

A portable coal mine rescue and survival equipment is reported that consists of a chlorate candle with a lithium hydroxide carbon-dioxide absorbent for oxygen generation, a breathing bag and tubing to conduct breathing to and from the man. A plastic hood incorporating a mouth piece for communication provides also eye protection and prevents inhalation through the nose. Manned testing of a prototype system demonstrated the feasibility of this closed circuit no-maintenance breathing apparatus that provides for good voice communication.

New Solid Polymer Electrolytes for Improved Lithium Batteries

NASA Technical Reports Server (NTRS)

Hehemann, David G.

2002-01-01

The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

A Novel and Generalized Lithium-Ion-Battery Configuration utilizing Al Foil as Both Anode and Current Collector for Enhanced Energy Density.

PubMed

Ji, Bifa; Zhang, Fan; Sheng, Maohua; Tong, Xuefeng; Tang, Yongbing

2017-02-01

A novel battery configuration based on an aluminum foil anode and a conventional cathode is developed. The aluminum foil plays a dual role as both the active anode material and the current collector, which enhances the energy density of the packaged battery, and reduces the production cost. This generalized battery configuration has high potential for application in next-generation lithium-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Near-IR, blue, and UV generation by frequency conversion of a Tm:YAP laser

NASA Astrophysics Data System (ADS)

Cole, Brian; Goldberg, Lew; Chinn, Steve

2018-02-01

We describe generation of near-infrared (944nm, 970nm), blue (472nm, 485nm), and UV (236 nm) light by frequency up-conversion of 2 μm output of a compact and efficient passively Q-switched Tm:YAP laser. The Tm:YAP laser source was near diffraction limited with maximum Q-switched pulse peak power of 190 kW. For second harmonic generation (SHG) of NIR, both periodically poled lithium niobate (PPLN) and lithium tri-borate (LBO) were evaluated, with 58% conversion efficiency and 3.1 W of 970 nm power achieved with PPLN. The PPLN 970nm emission was frequency doubled in 20mm long type I LBO, generating 1.1 W at 485nm with a conversion efficiency of 34%. With LBO used for frequency doubling of 2.3 W of 1888 nm Tm:YAP output to 944nm, 860mW was generated, with 37% conversion efficiency. Using a second LBO crystal to generate the 4th harmonic, 545mW of 472nm power was generated, corresponding to 64% conversion efficiency. To generate the 8th harmonic of Tm:YAP laser emission, the 472nm output of the second LBO was frequency doubled in a 7mm long BBO crystal, generating 110 mW at 236nm, corresponding to 21% conversion efficiency.

Recovery and recycling of lithium value from spent lithium titanate (Li2TiO3) pebbles

NASA Astrophysics Data System (ADS)

Mandal, D.

2013-09-01

In the first generation fusion reactors the fusion of deuterium (D) and tritium (T) is considered to produce energy to meet the future energy demand. Deuterium is available in nature whereas, tritium is not. Lithium-6 (Li6) isotope has the ability to produce tritium in the n, α nuclear reaction with neutrons. Thus lithium-based ceramics enriched by Li6 isotope are considered for the tritium generation for its use in future fusion reactors. Lithium titanate is one such Li-based ceramic material being considered for its some attractive properties viz., high thermal and chemical stability, high thermal conductivity, and low tritium solubility. It is reported in the literature, that the burn up of these pebbles in the fusion reactor will be limited to only 15-17 atomic percentage. At the end of life, the pebbles will contain more than 45% unused Li6 isotope. Due to the high cost of enriched Li6 and the waste disposal considerations, it is necessary to recover the unused Li from the spent lithium titanate pebbles. Till date, only the feasibilities of different processes are reported, but no process details are available. Experiments were carried out for the recovery of Li from simulated Li2TiO3 pebbles and to reuse of lithium in lithium titanate pebble fabrication. The details of the experiments and results are discussed in this paper. Simulated lithium titanate (Li2TiO3) pebbles. The objective of the study is to develop a process which can be used to recover lithium value form the spent Li2TiO3 pebbles from future fusion reactor. The Li2TiO3 pebbles used in the study were synthesized and fabricated by the solid state reaction process developed by Mandal et al. described in details somewhere else [1,2]. Spherical Li2TiO3 pebbles of size 1.0 mm were used and the properties of the Li2TiO3 pebbles used in the study are shown in Table 1. Hydrochloric acid (HCl), of 99.8% purity, purchased from Merck and Loba Chemicals, Mumbai, India. To leach lithium from Li2TiO3 Hydrochloric acid was used. The reasons to use hydrochloric acid are discussed below. Sodium carbonate (Na2CO3) analytical grade, procured form Merck Chemicals, Mumbai, India. To precipitate lithium as lithium carbonate from lithium hydroxide solution sodium carbonate was used. Distilled water. Distilled was used in the experiments, primarily to dilute hydrochloric acid to the desired molar solution. Leaching agent. Concentration of the leaching agent. Temperature. Speed of agitation. Solid to liquid ratio, and Particle Size. In the experimental work spherical Li2TiO3 pebbles of size 1.0 was used as mentioned above. To study the effect of particle size on the recovery of lithium from fine Li2TiO3 particles of size range 100-200 μm were used. These fines were obtained by pulverizing 1.0 mm Li2TiO3 pebbles in a planetary ball mill and classified standard sieves.It is reported that both HNO3 and HCl give relatively more recovery of lithium compared to H2SO4[11-13]. Though the handling of HCl is difficulties due to the chloride corrosion, it is preferred to HNO3 because the deposal of nitrate waste which will generate due to the latter's use viz. sodium nitrate is a problem as per the norms of pollution control standard [11,12].The leaching of Li2TiO3 pebbles were carried out in a 1000 ml three necked and flat bottom glass reactor. The flux was fitted with a reflux condenser to reduce the loss of solution by evaporation and a thermometer. The solid was suspended in the solution by stirring the solution using a magnetic stirrer. The flux was kept on a hot plate with a temperature controller to heat the slurry at constant temperature. The temperature of the solution was controlled within ±3 °C and the temperature of the slurry was noted at an interval of 5 min and the average temperature of each run is determined by time average of the noted readings.A known of volume of HCl solution with known concentration was added to the flux. After the desired stirring speed and reaction temperature were attained, the solid sample of 5 g was added to the solution in reactor. 5 ml solution was withdrawn and filtered after specific time for analyzing the concentration of lithium in the solution by Atomic Absorption Spectrophotometer (AAS) and 5 ml fresh lixiviant was added into the reactor immediately to maintain the volume of the solution constant.To obtain the optimum conditions, leaching experiments were tested under various conditions, i.e. changing speed of agitation, temperature, S/L ratio and concentration of the acid.

Experimental and theoretical screening of nanoscale oxide reactivity with LiBH4

NASA Astrophysics Data System (ADS)

Opalka, S. M.; Tang, X.; Laube, B. L.; Vanderspurt, T. H.

2009-05-01

Experimentation, thermodynamic modeling, and atomic modeling were combined to screen the reactivity of SiO2, Al2O3, and ZrO2 nanoscale oxides with LiBH4. Equilibrium thermodynamic modeling showed that the reactions of oxides with LiBH4 could lead to formation of stable Li-bearing oxide and metal boride phases. Experimentation was conducted to evaluate the discharge/recharge reaction products of nanoscale oxide-LiBH4 mixtures. Thermal gravimetric analyses-mass spectroscopy and x-ray diffraction revealed significant SiO2 destabilization of LiBH4 dehydrogenation, resulting in the formation of lithium silicate and boric acid. A smaller amount of lithium metaborate and boric acid was formed with Al2O3. No destabilization products were observed with ZrO2. Density functional theory atomic modeling predicted much stronger LiBH4 interfacial adsorption on the SiO2 and Al2O3 surfaces than on the ZrO2 surface, which was consistent with the experimental findings. Following dehydrogenation, interfacial Li atoms were predicted to strongly adsorb on the oxide surfaces effectively competing with LiH formation. The interfacial Li interactions with Al2O3 and ZrO2 were equal in strength in the fully hydrided and dehydrided states, so that their predicted net effect on LiBH4 dehydrogenation was insignificant. Zirconia was selected for nanoframework development based on the combined observations of compatibility and weaker associative interactions with LiBH4.

Towards Next Generation Lithium-Sulfur Batteries: Non-Conventional Carbon Compartments/Sulfur Electrodes and Multi-Scale Analysis

DOE PAGES

Dysart, Arthur D.; Burgos, Juan C.; Mistry, Aashutosh; ...

2016-02-09

In this work, a novel heterofunctional, bimodal-porous carbon morphology, termed the carbon compartment (CC), is utilized as a sulfur host as a lithium-sulfur battery cathode. A multi-scale model explores the physics and chemistry of the lithium-sulfur battery cathode. The CCs are synthesized by a rapid, low cost process to improve electrode-electrolyte interfacial contact and accommodate volumetric expansion associated with sulfide formation. The CCs demonstrate high sulfur loading (47 %-wt. S) and ca. 700 mAh g -1 reversible capacity with high coulombic efficiency due to their unique structures. Density functional theory and ab initio Molecular Dynamics characterize the interface between themore » C/S composite and electrolyte during the sulfur reduction mechanism. Stochastic realizations of 3D electrode microstructures are reconstructed based on representative SEM images to study the influence of solid sulfur loading and lithium sulfide precipitation on microstructural and electrochemical properties. A macroscale electrochemical performance model is developed to analyze the performance of lithium-sulfur batteries. The combined multi-scale simulation studies explain key fundamentals of sulfur reduction and its relation to the polysulfide shuttle mechanism: how the process is affected due to the presence of carbon substrate, thermodynamics of lithium sulfide formation and deposition on carbon, and microstructural effects on the overall cell performance.« less

Uranium, thorium and REE partitioning into sulfide liquids at high pressure and high temperature: Implications for reduced, S-rich planetary bodies

NASA Astrophysics Data System (ADS)

Wohlers, A.; Wood, B. J.

2017-12-01

Based on models of the young solar nebula it is likely that the inner planets went through an early reduced phase of accretion with high metal/silicate ratio and low volatile element contents. Mercury is an existing example of a large planetary embryo with these characteristics but also with a very high S content. In order to investigate the geochemical evolution of Mercury-like bodies we experimentally determined the partitioning of lithophile elements (U, Th, Eu, Sm, Nd, Zr, La, Ce, Yb) between sulfide liquid, low-S metals and silicate melt at 1.5 GPa and 1400-2100˚C. Our results, when combined with those of Wohlers and Wood (2015) show that under highly reducing conditions (FeOsilicate<1wt%) U, Sm, Nd and other lithophile elements partition strongly into FeS liquids relative to silicate melts. The dependences of D's on the FeS contents of the metal and FeO contents of the silicate may be understood in terms of exchange reactions: UO2 + 2FeS = 2FeO + US2silicate sulfide silicate sulfideHigh concentrations of FeSmetal and low FeO contents of the silicate melts drive the reaction to the right, yielding high US2 in the sulfide and high DU. A second effect which raises DU (and other lithophile D's) is the S content of the silicate melt. The latter increases rapidly at low FeO contents and reaches 11wt %. This greatly reduces the activity coefficient of FeO, displacing the reaction further to the right. At 1.5GPa and 1400˚C we obtain sulfide-silicate partitioning with DNd/DSm 1.4 and DTh 0.1DU. As temperature increases to 2100˚C, DNd/DSm declines to 1.0 and DTh/DU increases to 0.3. We estimated the effects of accreting a reduced sulfur-rich component (with FeS core) added to early Earth. The results at 1400˚C imply the possibility of a significant ( 11ppm) 142Nd anomaly in silicate Earth and the addition of >8 ppb U to the core, but require an unreasonably high Th/U of silicate Earth (4.54). Results at 2100˚C lead to a 142Nd anomaly of 0 but addition of such a reduced sulfur-rich body could add up to 10 ppb of U to the core, together with 21 ppb Th. This combination would generate 3 TW of the energy required for the geodynamo. In this case, the Th/U ratio of silicate Earth would be 4.3, within the range of some estimates. Wohlers A. & Wood B.J. (2015) A Mercury-like component of early Earth yield uranium in the core and high mantle Nd142. Nature 520, 337-340

Porous silicon confers bioactivity to polycaprolactone composites in vitro.

PubMed

Henstock, J R; Ruktanonchai, U R; Canham, L T; Anderson, S I

2014-04-01

Silicon is an essential element for healthy bone development and supplementation with its bioavailable form (silicic acid) leads to enhancement of osteogenesis both in vivo and in vitro. Porous silicon (pSi) is a novel material with emerging applications in opto-electronics and drug delivery which dissolves to yield silicic acid as the sole degradation product, allowing the specific importance of soluble silicates for biomaterials to be investigated in isolation without the elution of other ionic species. Using polycaprolactone as a bioresorbable carrier for porous silicon microparticles, we found that composites containing pSi yielded more than twice the amount of bioavailable silicic acid than composites containing the same mass of 45S5 Bioglass. When incubated in a simulated body fluid, the addition of pSi to polycaprolactone significantly increased the deposition of calcium phosphate. Interestingly, the apatites formed had a Ca:P ratio directly proportional to the silicic acid concentration, indicating that silicon-substituted hydroxyapatites were being spontaneously formed as a first order reaction. Primary human osteoblasts cultured on the surface of the composite exhibited peak alkaline phosphatase activity at day 14, with a proportional relationship between pSi content and both osteoblast proliferation and collagen production over 4 weeks. Culturing the composite with J744A.1 murine macrophages demonstrated that porous silicon does not elicit an immune response and may even inhibit it. Porous silicon may therefore be an important next generation biomaterial with unique properties for applications in orthopaedic tissue engineering.

Increased hippocampal, thalamus and amygdala volume in long-term lithium-treated bipolar I disorder patients compared with unmedicated patients and healthy subjects.

PubMed

López-Jaramillo, Carlos; Vargas, Cristian; Díaz-Zuluaga, Ana M; Palacio, Juan David; Castrillón, Gabriel; Bearden, Carrie; Vieta, Eduard

2017-02-01

Magnetic resonance imaging (MRI) studies in bipolar I disorder (BD-I) suggest that lithium is associated with increased volumes of cortico-limbic structures. However, more rigorous control of confounding factors is needed to obtain further support for this hypothesis. The aim of the present study was to assess differences in brain volumes among long-term lithium-treated BD-I patients, unmedicated BD-I patients, and healthy controls. This was a cross-sectional study with 32 euthymic BD-I patients (16 on lithium monotherapy for a mean of 180 months, and 16 receiving no medication for at least the 2 months prior to the study) and 20 healthy controls. Patients were euthymic (Hamilton Depression Rating Scale [HDRS] <6 and Young Mania Rating Scale [YMRS] <7) and had not taken psychotropic medications other than lithium for at least 6 months. Brain images were acquired on a 1.5 Tesla MRI (Phillips, Amsterdam, The Netherlands) and segmented to generate volumetric measures of cortical and subcortical brain areas, ventricles and global brain. Significant differences were found in the volumes of the left amygdala (P=.0003), right amygdala (P=.030), left hippocampus (P=.022), left thalamus (P=.022), and right thalamus (P=.019) in long-term lithium-treated BD-I patients, compared to unmedicated patients and controls, after multivariable adjustment. No differences were observed in global brain volume or in ventricular size among the three groups. Likewise, there was no correlation between serum lithium levels and the increase in size in the described brain areas. The structural differences found among the three groups, and specifically those between long-term lithium-treated and unmedicated BD-I patients, indicate increased limbic structure volumes in lithium-treated patients. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Heat transfer and thermal management studies of lithium polymer batteries for electric vehicle applications

NASA Astrophysics Data System (ADS)

Song, Li

The thermal conductivities of the polymer electrolyte and composite cathode are important parameters characterizing heat transport in lithium polymer batteries. The thermal conductivities of lithium polymer electrolytes, including poly-ethylene oxide (PEO), PEO-LiClO4, PEO-LiCF3SO 3, PEO-LiN(CF3SO2)2, PEO-LiC(CF 3SO2)3, and the thermal conductivities of TiS 2 and V6O13 composite cathodes, were measured over the temperature range from 25°C to 150°C by a guarded heat flow meter. The thermal conductivities of the electrolytes were found to be relatively constant for the temperature and for electrolytes with various concentrations of the lithium salt. The thermal conductivities of the composite cathodes were found to increase with the temperature below the melting temperature of the polymer electrolyte and only slightly increase above the melting temperature. Three different lithium polymer cells, including Li/PEO-LiCF3 S O3/TiS2, Li/PEO-LiC(CF3 S O2)3/V6 O13, and Li/PEO-LiN(CF3 S O2)2/ Li1+x Mn2 O4 were prepared and their discharge curves, along with heat generation rates, were measured at various galvanostatic discharge current densities, and at different temperature (70°C, 80°C and 90°C), by a potentiostat/galvanostat and an isothermal microcalorimeter. The thermal stability of a lithium polymer battery was examined by a linear perturbation analysis. In contrast to the thermal conductivity, the ionic conductivity of polymer electrolytes for lithium-polymer cell increases greatly with increasing temperature, an instability could arise from this temperature dependence. The numerical calculations, using a two dimensional thermal model, were carried out for constant potential drop across the electrolyte, for constant mean current density and for constant mean cell output power. The numerical calculations were approximately in agreement with the linear perturbation analysis. A coupled mathematical model, including electrochemical and thermal components, was developed to study the heat transfer and thermal management of lithium polymer batteries. The results calculated from the model, including temperature distributions, and temperatures at different stages of discharge are significantly different from those calculated from the thermal model. The discharge curves and heat generation rates calculated by the electrochemical-thermal model were in agreement with the experimental results. Different thermal management approaches, including a variable conductance insulation enclosure were studied.

High-power liquid-lithium jet target for neutron production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halfon, S.; Feinberg, G.; Racah Institute of Physics, Hebrew University, Jerusalem 91904

2013-12-15

A compact liquid-lithium target (LiLiT) was built and tested with a high-power electron gun at the Soreq Nuclear Research Center. The lithium target, to be bombarded by the high-intensity proton beam of the Soreq Applied Research Accelerator Facility (SARAF), will constitute an intense source of neutrons produced by the {sup 7}Li(p,n){sup 7}Be reaction for nuclear astrophysics research and as a pilot setup for accelerator-based Boron Neutron Capture Therapy. The liquid-lithium jet target acts both as neutron-producing target and beam dump by removing the beam thermal power (>5 kW, >1 MW/cm{sup 3}) with fast transport. The target was designed based onmore » a thermal model, accompanied by a detailed calculation of the {sup 7}Li(p,n) neutron yield, energy distribution, and angular distribution. Liquid lithium is circulated through the target loop at ∼200 °C and generates a stable 1.5 mm-thick film flowing at a velocity up to 7 m/s onto a concave supporting wall. Electron beam irradiation demonstrated that the liquid-lithium target can dissipate electron power areal densities of >4 kW/cm{sup 2} and volume power density of ∼2 MW/cm{sup 3} at a lithium flow of ∼4 m/s while maintaining stable temperature and vacuum conditions. The LiLiT setup is presently in online commissioning stage for high-intensity proton beam irradiation (1.91–2.5 MeV, 1–2 mA) at SARAF.« less

Multiple episodes of zeolite deposition in fractured silicic tuff

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carlos, B.A.; Chipera, S.J.; Snow, M.G.

Fractures in silicic tuffs above the water table at Yucca Mountain, Nevada, USA contain two morphologies of heulandite with different compositions. Tabular heulandite is zoned, with Sr-rich cores and Mg-rich rims. Later prismatic heulandite is nearly the same composition as the more magnesian rims. Heulandite and stellerite may occur between layers of calcite, and calcite occurs locally between generations of heulandite. Thermodynamic modeling, using estimated thermodynamic data and observed chemical compositions for heulandite and stellerite, shows that stellerite is the favored zeolite unless Ca concentrations are reduced or Mg and/or Sr concentrations are significantly elevated above current Yucca Mountain waters.

Tandem cyclopropanation with dibromomethane under Grignard conditions.

PubMed

Brunner, Gerhard; Eberhard, Laura; Oetiker, Jürg; Schröder, Fridtjof

2008-10-03

Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnesium and CH2Br2 under Barbier conditions at higher temperatures. The reaction rates depend on the substitution pattern of the (homo)allylic alcoholates and on the counterion with lithium giving best results. Good to excellent syn-selectivities are obtained from alpha-substituted substrates, which are in accord with a staggered Houk model. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.

Physical-chemical characterization and biological assessment of simple and lithium-doped biological-derived hydroxyapatite thin films for a new generation of metallic implants

NASA Astrophysics Data System (ADS)

Popescu, A. C.; Florian, P. E.; Stan, G. E.; Popescu-Pelin, G.; Zgura, I.; Enculescu, M.; Oktar, F. N.; Trusca, R.; Sima, L. E.; Roseanu, A.; Duta, L.

2018-05-01

We report on the synthesis by PLD of simple and lithium-doped biological-origin hydroxyapatite (HA) films. The role of doping reagents (Li2CO3, Li3PO4) on the morphology, structure, chemical composition, bonding strength and cytocompatibility of the films was investigated. SEM investigations of the films evidenced a surface morphology consisting of particles with mean diameters of (5-7) μm. GIXRD analyses demonstrated that the synthesized structures consisted of HA phase only, with different degrees of crystallinity, mainly influenced by the doping reagent type. After only three days of immersion in simulated body fluid, FTIR spectra showed a remarkable growth of a biomimetic apatitic film, indicative of a high biomineralization capacity of the coatings. EDS analyses revealed a quasi-stoichiometric target-to-substrate transfer, the values inferred for the Ca/P ratio corresponding to a biological apatite. All synthesized structures displayed a hydrophilic behavior, suitable for attachment of osteoblast cells. In vitro cell viability tests showed that the presence of Li2CO3 and Li3PO4 as doping reagents promoted the hMSC growth on film surfaces. Taking into consideration these enhanced characteristics, corroborated with a low fabrication cost generated by sustainable resources, one should consider the lithium-doped biological-derived materials as promising prospective solutions for a next generation of coated implants with rapid osteointegration.

Genetic variants associated with response to lithium treatment in bipolar disorder: a genome-wide association study.

PubMed

Hou, Liping; Heilbronner, Urs; Degenhardt, Franziska; Adli, Mazda; Akiyama, Kazufumi; Akula, Nirmala; Ardau, Raffaella; Arias, Bárbara; Backlund, Lena; Banzato, Claudio E M; Benabarre, Antoni; Bengesser, Susanne; Bhattacharjee, Abesh Kumar; Biernacka, Joanna M; Birner, Armin; Brichant-Petitjean, Clara; Bui, Elise T; Cervantes, Pablo; Chen, Guo-Bo; Chen, Hsi-Chung; Chillotti, Caterina; Cichon, Sven; Clark, Scott R; Colom, Francesc; Cousins, David A; Cruceanu, Cristiana; Czerski, Piotr M; Dantas, Clarissa R; Dayer, Alexandre; Étain, Bruno; Falkai, Peter; Forstner, Andreas J; Frisén, Louise; Fullerton, Janice M; Gard, Sébastien; Garnham, Julie S; Goes, Fernando S; Grof, Paul; Gruber, Oliver; Hashimoto, Ryota; Hauser, Joanna; Herms, Stefan; Hoffmann, Per; Hofmann, Andrea; Jamain, Stephane; Jiménez, Esther; Kahn, Jean-Pierre; Kassem, Layla; Kittel-Schneider, Sarah; Kliwicki, Sebastian; König, Barbara; Kusumi, Ichiro; Lackner, Nina; Laje, Gonzalo; Landén, Mikael; Lavebratt, Catharina; Leboyer, Marion; Leckband, Susan G; Jaramillo, Carlos A López; MacQueen, Glenda; Manchia, Mirko; Martinsson, Lina; Mattheisen, Manuel; McCarthy, Michael J; McElroy, Susan L; Mitjans, Marina; Mondimore, Francis M; Monteleone, Palmiero; Nievergelt, Caroline M; Nöthen, Markus M; Ösby, Urban; Ozaki, Norio; Perlis, Roy H; Pfennig, Andrea; Reich-Erkelenz, Daniela; Rouleau, Guy A; Schofield, Peter R; Schubert, K Oliver; Schweizer, Barbara W; Seemüller, Florian; Severino, Giovanni; Shekhtman, Tatyana; Shilling, Paul D; Shimoda, Kazutaka; Simhandl, Christian; Slaney, Claire M; Smoller, Jordan W; Squassina, Alessio; Stamm, Thomas; Stopkova, Pavla; Tighe, Sarah K; Tortorella, Alfonso; Turecki, Gustavo; Volkert, Julia; Witt, Stephanie; Wright, Adam; Young, L Trevor; Zandi, Peter P; Potash, James B; DePaulo, J Raymond; Bauer, Michael; Reininghaus, Eva Z; Novák, Tomas; Aubry, Jean-Michel; Maj, Mario; Baune, Bernhard T; Mitchell, Philip B; Vieta, Eduard; Frye, Mark A; Rybakowski, Janusz K; Kuo, Po-Hsiu; Kato, Tadafumi; Grigoroiu-Serbanescu, Maria; Reif, Andreas; Del Zompo, Maria; Bellivier, Frank; Schalling, Martin; Wray, Naomi R; Kelsoe, John R; Alda, Martin; Rietschel, Marcella; McMahon, Francis J; Schulze, Thomas G

2016-03-12

Lithium is a first-line treatment in bipolar disorder, but individual response is variable. Previous studies have suggested that lithium response is a heritable trait. However, no genetic markers of treatment response have been reproducibly identified. Here, we report the results of a genome-wide association study of lithium response in 2563 patients collected by 22 participating sites from the International Consortium on Lithium Genetics (ConLiGen). Data from common single nucleotide polymorphisms (SNPs) were tested for association with categorical and continuous ratings of lithium response. Lithium response was measured using a well established scale (Alda scale). Genotyped SNPs were used to generate data at more than 6 million sites, using standard genomic imputation methods. Traits were regressed against genotype dosage. Results were combined across two batches by meta-analysis. A single locus of four linked SNPs on chromosome 21 met genome-wide significance criteria for association with lithium response (rs79663003, p=1·37 × 10(-8); rs78015114, p=1·31 × 10(-8); rs74795342, p=3·31 × 10(-9); and rs75222709, p=3·50 × 10(-9)). In an independent, prospective study of 73 patients treated with lithium monotherapy for a period of up to 2 years, carriers of the response-associated alleles had a significantly lower rate of relapse than carriers of the alternate alleles (p=0·03268, hazard ratio 3·8, 95% CI 1·1-13·0). The response-associated region contains two genes for long, non-coding RNAs (lncRNAs), AL157359.3 and AL157359.4. LncRNAs are increasingly appreciated as important regulators of gene expression, particularly in the CNS. Confirmed biomarkers of lithium response would constitute an important step forward in the clinical management of bipolar disorder. Further studies are needed to establish the biological context and potential clinical utility of these findings. Deutsche Forschungsgemeinschaft, National Institute of Mental Health Intramural Research Program. Copyright © 2016 Elsevier Ltd. All rights reserved.

Probing the atomic structure of basaltic melts generated by partial melting of upper mantle peridotite (KLB-1): Insights from high-resolution solid-state NMR study

NASA Astrophysics Data System (ADS)

Park, S. Y.; Lee, S. K.

2015-12-01

Probing the structural disorder in multi-component silicate glasses and melts with varying composition is essential to reveal the change of macroscopic properties in natural silicate melts. While a number of NMR studies for the structure of multi-component silicate glasses and melts including basaltic and andesitic glasses have been reported (e.g., Park and Lee, Geochim. Cosmochim. Acta, 2012, 80, 125; Park and Lee, Geochim. Cosmochim. Acta, 2014, 26, 42), many challenges still remain. The composition of multi-component basaltic melts vary with temperature, pressure, and melt fraction (Kushiro, Annu. Rev. Earth Planet. Sci., 2001, 71, 107). Especially, the eutectic point (the composition of first melt) of nepheline-forsterite-quartz (the simplest model of basaltic melts) moves with pressure from silica-saturated to highly undersaturated and alkaline melts. The composition of basaltic melts generated by partial melting of upper mantle peridotite (KLB-1, the xenolith from Kilbourne Hole) also vary with pressure. In this study we report experimental results for the effects of composition on the atomic structure of Na2O-MgO-Al2O3-SiO2 (NMAS) glasses in nepheline (NaAlSiO4)-forsterite (Mg2SiO4)-quartz (SiO2) eutectic composition and basaltic glasses generated by partial melting of upper mantle peridotite (KLB-1) using high-resolution multi-nuclear solid-state NMR. The Al-27 3QMAS (triple quantum magic angle spinning) NMR spectra of NMAS glasses in nepheline-forsterite-quartz eutectic composition show only [4]Al. The Al-27 3QMAS NMR spectra of KLB-1 basaltic glasses show mostly [4]Al and a non-negligible fraction of [5]Al. The fraction of [5]Al, the degree of configurational disorder, increases from 0 at XMgO [MgO/(MgO+Al2O3)]=0.55 to ~3% at XMgO=0.79 in KLB-1 basaltic glasses while only [4]Al are observed in nepheline-forsterite-quartz eutectic composition. The current experimental results provide that the fraction of [5]Al abruptly increases by the effect of composition as well as pressure in natural silicate melts. The changes of the fraction of highly coordinated Al in multi-component silicate glasses and melts with composition can provide insight into the changes of macroscopic properties (e.g., entropy, viscosity, and diffusivity) with varying composition of melt.

Dentin-cement Interfacial Interaction

PubMed Central

Atmeh, A.R.; Chong, E.Z.; Richard, G.; Festy, F.; Watson, T.F.

2012-01-01

The interfacial properties of a new calcium-silicate-based coronal restorative material (Biodentine™) and a glass-ionomer cement (GIC) with dentin have been studied by confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), micro-Raman spectroscopy, and two-photon auto-fluorescence and second-harmonic-generation (SHG) imaging. Results indicate the formation of tag-like structures alongside an interfacial layer called the “mineral infiltration zone”, where the alkaline caustic effect of the calcium silicate cement’s hydration products degrades the collagenous component of the interfacial dentin. This degradation leads to the formation of a porous structure which facilitates the permeation of high concentrations of Ca2+, OH-, and CO32- ions, leading to increased mineralization in this region. Comparison of the dentin-restorative interfaces shows that there is a dentin-mineral infiltration with the Biodentine, whereas polyacrylic and tartaric acids and their salts characterize the penetration of the GIC. A new type of interfacial interaction, “the mineral infiltration zone”, is suggested for these calcium-silicate-based cements. PMID:22436906

Tailoring entanglement through domain engineering in a lithium niobate waveguide

PubMed Central

Ming, Yang; Tan, Ai-Hong; Wu, Zi-Jian; Chen, Zhao-Xian; Xu, Fei; Lu, Yan-Qing

2014-01-01

We propose to integrate the electro-optic (EO) tuning function into on-chip domain engineered lithium niobate (LN) waveguide. Due to the versatility of LN, both the spontaneously parametric down conversion (SPDC) and EO interaction could be realized simultaneously. Photon pairs are generated through SPDC, and the formation of entangled state is modulated by EO processes. An EO tunable polarization-entangled photon state is proposed. Orthogonally-polarized and parallel-polarized entanglements of photon pairs are instantly switchable by tuning the applied field. The characteristics of the source are theoretically investigated showing adjustable bandwidths and high entanglement degrees. Moreover, other kinds of reconfigurable entanglement are also achievable based on suitable domain-design. We believe tailoring entanglement based on domain engineering is a very promising solution for next generation function-integrated quantum circuits. PMID:24770555

Micromechanical Modeling of Storage Particles in Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Purkayastha, Rajlakshmi Tarun

The effect of stress on storage particles within a lithium ion battery, while acknowledged, is not understood very well. In this work three non-dimensional parameters were identified which govern the stress response within a spherical storage particle. These parameters are developed using material properties such as the diffusion coefficient, particle radius, partial molar volume and Young's modulus. Stress maps are then generated for various values of these parameters for fixed rates of insertion, applying boundary conditions similar to those found in a battery. Stress and concentration profiles for various values of these parameters show the coupling between stress and concentration is magnified depending on the values of the parameters. These maps can be used for different materials, depending on the value of the dimensionless parameters. The value of maximum stress generated is calculated for extraction as well as insertion of lithium into the particle. The model was then used to study to ellipsoidal particles in order to ascertain the effect of geometry on the maximum stress within the particle. By performing a parameter study, we can identify those materials for which particular aspect ratios of ellipsoids are more beneficial, in terms of reducing stress. We find that the stress peaks at certain aspect ratios, mostly at 2 and 1/ 2 . A parameter study was also performed on cubic particle. The values of maximum stresses for both insertion and extraction of lithium were plotted as contour plots. It was seen that the material parameters influenced the location of the maximum stress, with the maximum stress occurring either at the center of the edge between two faces or the point at the center of a face. Newer materials such as silicon are being touted as new lithium storage materials for batteries due to their higher capacity. Their tendency to rapidly loose capacity in a short period of time has led to a variety designs such are the use of carbon nanotubes or the use of coatings in order to mitigate the large expansion and stresses, which leads to spalling off of the material. We therefore extended the results for spherical storage particles to include the presence of an additional layer of material surrounding the storage particle. We perform a parameter study to see at which material properties are most beneficial in reducing stresses within the particle, and the results were tabulated. It was seen that thicker layers can lead to mitigation in the value of maximum stresses. A simple fracture analysis was carried out and the material parameters which would most likely cause crack growth to occur were identified. Finally an integrated 2-D model of a lithium ion battery was developed to study the mechanical stress in storage particles as a function of material properties. The effect of morphology on the stress and lithium concentration is studied for the case of extraction of lithium in terms of the previously developed non-dimensional parameters. Both, particles functioning in isolation were studied, as well as in closely-packed systems. The results show that the particle distance from the separator, in combination with the material properties of the particle, is critical in predicting the stress generated within the particle.

Suitability assessment of grey water quality treated with an upflow-downflow siliceous sand/marble waste filtration system for agricultural and industrial purposes.

PubMed

Chaabane, Safa; Riahi, Khalifa; Hamrouni, Hédi; Thayer, Béchir Ben

2017-04-01

The present study examines the suitability assessment of an upflow-downflow siliceous sand/marble waste filtration system for treatment and reuse of grey water collected from bathrooms of the student residential complex at the Higher Institute of Engineering Medjez El Bab (Tunisia). Once the optimization of grey water pre-treatment system has been determined, the filtration system was operated at different hydraulic loading rate and media filter proportions in order to assess the suitability of treated grey water for irrigational purpose according to salinity hazard, sodium hazard, magnesium hazard, permeability index, water infiltration rate, and widely used graphical methods. Suitability of the treated grey water for industrial purpose was evaluated in terms of foaming, corrosion, and scaling. Under optimal operational conditions, results reveals that treated grey water samples with an upflow-downflow siliceous sand/marble waste filtration system may be considered as a good and an excellent water quality suitable for irrigation purpose. However, treated grey water was found not appropriate for industrial purpose due to high concentrations of calcium and sodium that can generate foaming and scaling harm to boilers. These results suggest that treated grey water with an upflow-downflow siliceous sand/marble waste filtration system would support production when used as irrigation water.

Water quality characterization in some birimian aquifers of the Birim Basin, Ghana

USGS Publications Warehouse

Bruce, B.-Y.; Yidana, S.M.; Anku, Y.; Akabzaa, T.; Asiedu, D.

2009-01-01

The objective of this study was to determine the main controls on the hydrochemistry of groundwater in the study area. Mass balance modeling was used simultaneously with multivariate R-mode hierarchical cluster analysis to determine the significant sources of variation in the hydrochemistry. Two water types have been revealed in this area: (1) waters influenced more significantly by the weathering of silicate minerals from the underlying geology, and are rich in silica, sodium, calcium, bicarbonate, and magnesium ions, and (2) waters that have been influenced by the effects of fertilizers and other anthropogenic activities in the area. Mineral speciation and silicate mineral stability diagrams generated from the data suggest that montmorillonite, probably derived from the incongruent dissolution of feldspars and micas, is the most stable silicate phase in the groundwater. The apparent incongruent weathering of silicate minerals in the groundwater system has led to the enrichment of sodium, calcium, magnesium and bicarbonate ions as well as silica, leading to the supersaturation of calcite, aragonite, dolomite and quartz. Stability in the montmorillonite field suggests restricted flow conditions whereby groundwater residence time is relatively high, leading to greater contact of groundwater with the rock to enhance weathering. Cation exchange processes have also been determined to play minor roles in the hydrochemistry.

Influence of silica matrix composition and functional component additives on the bioactivity and viability of encapsulated living cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savage, Travis J.; Dunphy, Darren R.; Harbaugh, Svetlana

The remarkable impact encapsulation matrix chemistry can have on the bioactivity and viability of integrated living cells is reported. Two silica chemistries (aqueous silicate and alkoxysilane), and a functional component additive (glycerol), are employed to generate three distinct silica matrices. These matrices are used to encapsulate living E. coli cells engineered with a synthetic riboswitch for cell-based biosensing. Following encapsulation, membrane integrity, reproductive capability, and riboswitch-based protein expression levels and rates are measured over a 5 week period. Striking differences in E. coli bioactivity, viability, and biosensing performance are observed for cells encapsulated within the different matrices. E. coli cellsmore » encapsulated for 35 days in aqueous silicate-based (AqS) matrices showed relatively low membrane integrity, but high reproductive capability in comparison to cells encapsulated in glycerol containing sodium silicate-based (AqS + g) and alkoxysilane-based (PGS) gels. Further, cells in sodium silicate-based matrices showed increasing fluorescence output over time, resulting in a 1.8-fold higher fluorescence level, and a faster expression rate, over cells free in solution. Furthermore, this unusual and unique combination of biological properties demonstrates that careful design of the encapsulation matrix chemistry can improve functionality of the biocomposite material, and result in new and unexpected physiological states.« less

Influence of silica matrix composition and functional component additives on the bioactivity and viability of encapsulated living cells

DOE PAGES

Savage, Travis J.; Dunphy, Darren R.; Harbaugh, Svetlana; ...

2015-11-06

The remarkable impact encapsulation matrix chemistry can have on the bioactivity and viability of integrated living cells is reported. Two silica chemistries (aqueous silicate and alkoxysilane), and a functional component additive (glycerol), are employed to generate three distinct silica matrices. These matrices are used to encapsulate living E. coli cells engineered with a synthetic riboswitch for cell-based biosensing. Following encapsulation, membrane integrity, reproductive capability, and riboswitch-based protein expression levels and rates are measured over a 5 week period. Striking differences in E. coli bioactivity, viability, and biosensing performance are observed for cells encapsulated within the different matrices. E. coli cellsmore » encapsulated for 35 days in aqueous silicate-based (AqS) matrices showed relatively low membrane integrity, but high reproductive capability in comparison to cells encapsulated in glycerol containing sodium silicate-based (AqS + g) and alkoxysilane-based (PGS) gels. Further, cells in sodium silicate-based matrices showed increasing fluorescence output over time, resulting in a 1.8-fold higher fluorescence level, and a faster expression rate, over cells free in solution. Furthermore, this unusual and unique combination of biological properties demonstrates that careful design of the encapsulation matrix chemistry can improve functionality of the biocomposite material, and result in new and unexpected physiological states.« less

Diagnostic examination of thermally abused high-power lithium-ion cells

NASA Astrophysics Data System (ADS)

Abraham, D. P.; Roth, E. P.; Kostecki, R.; McCarthy, K.; MacLaren, S.; Doughty, D. H.

The inherent thermal instability of lithium-ion cells is a significant impediment to their widespread commercialization for hybrid-electric vehicle applications. Cells containing conventional organic electrolyte-based chemistries are prone to thermal runaway at temperatures around 180 °C. We conducted accelerating rate calorimetry measurements on high-power 18650-type lithium-ion cells in an effort to decipher the sequence of events leading to thermal runaway. In addition, electrode and separator samples harvested from a cell that was heated to 150 °C then air-quenched to room temperature were examined by microscopy, spectroscopy, and diffraction techniques. Self-heating of the cell began at 84 °C. The gases generated in the cell included CO 2 and CO, and smaller quantities of H 2, C 2H 4, CH 4, and C 2H 6. The main changes on cell heating to 150 °C were observed on the anode surface, which was covered by a thick layer of surface deposits that included LiF and inorganic and organo-phosphate compounds. The sources of gas generation and the mechanisms leading to the formation of compounds observed on the electrode surfaces are discussed.

Polysulfides capture-copper additive for long cycle life lithium sulfur batteries

DOE PAGES

Jia, Lei; Wu, Tianpin; Lu, Jun; ...

2016-10-18

Copper powder was introduced into the lithium sulfur battery system to capture intermediate polysulfides and Cu xS (x = 1 or 2) species was generated depending on the chain length of polysulfides. This phenomenon was verified by X-ray absorption near edge structure technique. The results indicated that copper can be oxidized to CuS by Li 2S x (x ≥ 6), and a mixture of Cu 2S and CuS was obtained when x ranges from 3 to 6. While Cu 2S is eventually formed in the presence of Li 2S 3. After several cycles activation, the polysulfide-shuttle effect and self-discharge phenomenonmore » which hinder the application of lithium sulfur batteries are found nearly eliminated Further experiments demonstrated that in the case of Cu 2S generation, a high specific sulfur capacity of 1300 mAh g –1 could be delivered, corresponding to 77.6% sulfur utilization, while the Coulombic efficiency approximates around 100%. As a result, self-discharge experiment further demonstrated that polysulfides almost disappear in the electrolyte, which verified the polysulfide-capture capability of copper.« less

Hierarchical columnar silicon anode structures for high energy density lithium sulfur batteries

NASA Astrophysics Data System (ADS)

Piwko, Markus; Kuntze, Thomas; Winkler, Sebastian; Straach, Steffen; Härtel, Paul; Althues, Holger; Kaskel, Stefan

2017-05-01

Silicon is a promising anode material for next generation lithium secondary batteries. To significantly increase the energy density of state of the art batteries with silicon, new concepts have to be developed and electrode structuring will become a key technology. Structuring is essential to reduce the macroscopic and microscopic electrode deformation, caused by the volume change during cycling. We report pulsed laser structuring for the generation of hierarchical columnar silicon films with outstanding high areal capacities up to 7.5 mAh cm-2 and good capacity retention. Unstructured columnar electrodes form a micron-sized block structure during the first cycle to compensate the volume expansion leading to macroscopic electrode deformation. At increased silicon loading, without additional structuring, pronounced distortion and the formation of cracks through the current collector causes cell failure. Pulsed laser ablation instead is demonstrated to avoid macroscopic electrode deformation by initial formation of the block structure. A full cell with lithiated silicon versus a carbon-sulfur cathode is assembled with only 15% overbalanced anode and low electrolyte amount (8 μl mgsulfur-1). While the capacity retention over 50 cycles is identical to a cell with high excess lithium anode, the volumetric energy density could be increased by 30%.

Electro-thermal analysis of Lithium Iron Phosphate battery for electric vehicles

NASA Astrophysics Data System (ADS)

Saw, L. H.; Somasundaram, K.; Ye, Y.; Tay, A. A. O.

2014-03-01

Lithium ion batteries offer an attractive solution for powering electric vehicles due to their relatively high specific energy and specific power, however, the temperature of the batteries greatly affects their performance as well as cycle life. In this work, an empirical equation characterizing the battery's electrical behavior is coupled with a lumped thermal model to analyze the electrical and thermal behavior of the 18650 Lithium Iron Phosphate cell. Under constant current discharging mode, the cell temperature increases with increasing charge/discharge rates. The dynamic behavior of the battery is also analyzed under a Simplified Federal Urban Driving Schedule and it is found that heat generated from the battery during this cycle is negligible. Simulation results are validated with experimental data. The validated single cell model is then extended to study the dynamic behavior of an electric vehicle battery pack. The modeling results predict that more heat is generated on an aggressive US06 driving cycle as compared to UDDS and HWFET cycle. An extensive thermal management system is needed for the electric vehicle battery pack especially during aggressive driving conditions to ensure that the cells are maintained within the desirable operating limits and temperature uniformity is achieved between the cells.

Interfacial instability of amorphous LiPON against lithium: A combined Density Functional Theory and spectroscopic study

NASA Astrophysics Data System (ADS)

Sicolo, Sabrina; Fingerle, Mathias; Hausbrand, René; Albe, Karsten

2017-06-01

The chemical instability of the glassy solid electrolyte LiPON against metallic lithium and the occurrence of side reactions at their interface is investigated by combining a surface science approach and quantum-mechanical calculations. Using an evolutionary structure search followed by a melt-quenching protocol, a model for the disordered structure of LiPON is generated and put into contact with lithium. Even the static optimization of a simple model interface suggests that the diffusion of lithium into LiPON is driven by a considerable driving force that could easily take place under experimental conditions. Calculated reaction energies indicate that the reduction and decomposition of LiPON is thermodynamically favorable. By monitoring the evolution of the LiPON core levels as a function of lithium exposure, the disruption of the LiPON network alongside the occurrence of new phases is observed. The direct comparison between UV photoelectron spectroscopy measurements and calculated electronic densities of states for increasing stages of lithiation univocally identifies the new phases as Li2O, Li3P and Li3N. These products are stable against Li metal and form a passivation layer which shields the electrolyte from further decomposition while allowing for the diffusion of Li ions.

Polysulfide-Scission Reagents for the Suppression of the Shuttle Effect in Lithium-Sulfur Batteries.

PubMed

Hua, Wuxing; Yang, Zhi; Nie, Huagui; Li, Zhongyu; Yang, Jizhang; Guo, Zeqing; Ruan, Chunping; Chen, Xi'an; Huang, Shaoming

2017-02-28

Lithium-sulfur batteries have become an appealing candidate for next-generation energy-storage technologies because of their low cost and high energy density. However, one of their major practical problems is the high solubility of long-chain lithium polysulfides and their infamous shuttle effect, which causes low Coulombic efficiency and sulfur loss. Here, we introduced a concept involving the dithiothreitol (DTT) assisted scission of polysulfides into lithium-sulfur system. Our designed porous carbon nanotube/S cathode coupling with a lightweight graphene/DTT interlayer (PCNTs-S@Gra/DTT) exhibited ultrahigh cycle-ability even at 5 C over 1100 cycles, with a capacity degradation rate of 0.036% per cycle. Additionally, the PCNTs-S@Gra/DTT electrode with a 3.51 mg cm -2 sulfur mass loading delivered a high initial areal capacity of 5.29 mAh cm -2 (1509 mAh g -1 ) at current density of 0.58 mA cm -2 , and the reversible areal capacity of the cell was maintained at 3.45 mAh cm -2 (984 mAh g -1 ) over 200 cycles at a higher current density of 1.17 mA cm -2 . Employing this molecule scission principle offers a promising avenue to achieve high-performance lithium-sulfur batteries.

Enhanced lithium storage capability of Li3V2(PO4)3@C co-modified with graphene and Ce3+ doping as high-power cathode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tong, Junjie; Fang, Yunhui

2017-12-01

As a high-voltage cathode material, monoclinic Li3V2(PO4)3 has been proposed as the next-generation commercial electrode for lithium-ion batteries. Nevertheless, it remains a practical challenge to improve the poor electronic conductivity of Li3V2(PO4)3. Herein, we first design and fabricate the Li3V2(PO4)3@C (LVP@C) nanocrystals further modified by graphene and doped with Ce3+-ion via a facile sol-gel method. The Ce3+ doping can form a continuous conductive pathway in the electrode and thus improve the intrinsic electronic conductivity of Li3V2(PO4)3 material. Meanwhile, the residual carbon layer and graphene can also construct a conductive network, which is helpful to enhance the apparent conductivity of Li3V2(PO4)3. Therefore, the graphene and Ce3+ doping co-decorated LVP@C (G-LVCeP@C) composite exhibits better lithium storage capability than the LVP@C and Ce3+-doped LVP@C (LVCeP@C) materials. This novel design provides an effective strategy for the preparation of other electrodes for lithium-ion batteries.

Distinguishing Biologically Relevant Hexoses by Water Adduction to the Lithium-Cationized Molecule.

PubMed

Campbell, Matthew T; Chen, Dazhe; Wallbillich, Nicholas J; Glish, Gary L

2017-10-03

A method to distinguish the four most common biologically relevant underivatized hexoses, d-glucose, d-galactose, d-mannose, and d-fructose, using only mass spectrometry with no prior separation/derivatization step has been developed. Electrospray of a solution containing hexose and a lithium salt generates [Hexose+Li] + . The lithium-cationized hexoses adduct water in a quadrupole ion trap. The rate of this water adduction reaction can be used to distinguish the four hexoses. Additionally, for each hexose, multiple lithiation sites are possible, allowing for multiple structures of [Hexose+Li] + . Electrospray produces at least one structure that reacts with water and at least one that does not. The ratio of unreactive lithium-cationized hexose to total lithium-cationized hexose is unique for the four hexoses studied, providing a second method for distinguishing the isomers. Use of the water adduction reaction rate or the unreactive ratio provides two separate methods for confidently (p ≤ 0.02) distinguishing the most common biologically relevant hexoses using only femtomoles of hexose. Additionally, binary mixtures of glucose and fructose were studied. A calibration curve was created by measuring the reaction rate of various samples with different ratios of fructose and glucose. The calibration curve was used to accurately measure the percentage of fructose in three samples of high fructose corn syrup (<4% error).

Self-pinched lithium beam transport experiments on SABRE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanson, D.L.; Olson, C.L.; Poukey, J.W.

Self-pinched transport of ion beams has many advantages for ion-driven ICF applications involving high yield and energy production. The authors are currently preparing for a self-pinched lithium beam transport experiment on the SABRE accelerator. There are three transport elements that must eventually be demonstrated: (1) efficient lithium beam generation and ballistic transport to a focus at the self-pinched transport channel entrance; (2) self-pinched transport in the channel, requiring optimized injection conditions and gas breakdown; and (3) self-pinched transport of the equilibrated beam from the channel into free space, with associated aiming and stability considerations. In the present experiment, a hollowmore » annular lithium beam from an applied-B extraction ion diode will be focused to small radius (r {le} 2 cm) in a 60 cm long ballistic focus section containing argon gas at a pressure of a few Torr. The self-pinched transport channel will contain a low pressure background gas of 10--40 mTorr argon to allow sufficient net current to confine the beam for long distance transport. IPROP simulations are in progress to optimize the design of the ballistic and self-pinched transport sections. Progress on preparation of this lithium self-pinched transport experiment, including a discussion of transport system design, important gas breakdown issues, and diagnostics, will be presented.« less

Nanostructured silicon anodes for lithium ion rechargeable batteries.

PubMed

Teki, Ranganath; Datta, Moni K; Krishnan, Rahul; Parker, Thomas C; Lu, Toh-Ming; Kumta, Prashant N; Koratkar, Nikhil

2009-10-01

Rechargeable lithium ion batteries are integral to today's information-rich, mobile society. Currently they are one of the most popular types of battery used in portable electronics because of their high energy density and flexible design. Despite their increasing use at the present time, there is great continued commercial interest in developing new and improved electrode materials for lithium ion batteries that would lead to dramatically higher energy capacity and longer cycle life. Silicon is one of the most promising anode materials because it has the highest known theoretical charge capacity and is the second most abundant element on earth. However, silicon anodes have limited applications because of the huge volume change associated with the insertion and extraction of lithium. This causes cracking and pulverization of the anode, which leads to a loss of electrical contact and eventual fading of capacity. Nanostructured silicon anodes, as compared to the previously tested silicon film anodes, can help overcome the above issues. As arrays of silicon nanowires or nanorods, which help accommodate the volume changes, or as nanoscale compliant layers, which increase the stress resilience of silicon films, nanoengineered silicon anodes show potential to enable a new generation of lithium ion batteries with significantly higher reversible charge capacity and longer cycle life.

The mixed alkali effect in ionically conducting glasses revisited: a study by molecular dynamics simulation.

PubMed

Habasaki, Junko; Ngai, Kia L

2007-09-07

When more than two kinds of mobile ions are mixed in ionic conducting glasses and crystals, there is a non-linear decrease of the transport coefficients of either type of ion. This phenomenon is known as the mixed mobile ion effect or Mixed Alkali Effect (MAE), and remains an unsolved problem. We use molecular dynamics simulation to study the complex ion dynamics in ionically conducting glasses including the MAE. In the mixed alkali lithium-potassium silicate glasses and related systems, a distinct part of the van Hove functions reveals that jumps from one kind of site to another are suppressed. Although, consensus for the existence of preferential jump paths for each kind of mobile ions seems to have been reached amongst researchers, the role of network formers and the number of unoccupied ion sites remain controversial in explaining the MAE. In principle, these factors when incorporated into a theory can generate the MAE, but in reality they are not essential for a viable explanation of the ion dynamics and the MAE. Instead, dynamical heterogeneity and "cooperativity blockage" originating from ion-ion interaction and correlation are fundamental for the observed ion dynamics and the MAE. Suppression of long range motion with increased back-correlated motions is shown to be a cause of the large decrease of the diffusivity especially in dilute foreign alkali regions. Support for our conclusion also comes from the fact that these features of ion dynamics are common to other ionic conductors, which have no glassy networks, and yet they all exhibit the MAE.

Promising Cell Configuration for Next-Generation Energy Storage: Li2S/Graphite Battery Enabled by a Solvate Ionic Liquid Electrolyte.

PubMed

Li, Zhe; Zhang, Shiguo; Terada, Shoshi; Ma, Xiaofeng; Ikeda, Kohei; Kamei, Yutaro; Zhang, Ce; Dokko, Kaoru; Watanabe, Masayoshi

2016-06-29

Lithium-ion sulfur batteries with a [graphite|solvate ionic liquid electrolyte|lithium sulfide (Li2S)] structure are developed to realize high performance batteries without the issue of lithium anode. Li2S has recently emerged as a promising cathode material, due to its high theoretical specific capacity of 1166 mAh/g and its great potential in the development of lithium-ion sulfur batteries with a lithium-free anode such as graphite. Unfortunately, the electrochemical Li(+) intercalation/deintercalation in graphite is highly electrolyte-selective: whereas the process works well in the carbonate electrolytes inherited from Li-ion batteries, it cannot take place in the ether electrolytes commonly used for Li-S batteries, because the cointercalation of the solvent destroys the crystalline structure of graphite. Thus, only very few studies have focused on graphite-based Li-S full cells. In this work, simple graphite-based Li-S full cells were fabricated employing electrolytes beyond the conventional carbonates, in combination with highly loaded Li2S/graphene composite cathodes (Li2S loading: 2.2 mg/cm(2)). In particular, solvate ionic liquids can act as a single-phase electrolyte simultaneously compatible with both the Li2S cathode and the graphite anode and can further improve the battery performance by suppressing the shuttle effect. Consequently, these lithium-ion sulfur batteries show a stable and reversible charge-discharge behavior, along with a very high Coulombic efficiency.

Electrochemistry and the Earth's Core-Mantle Boundary

NASA Astrophysics Data System (ADS)

Kavner, A.; Walker, D.

2001-12-01

The Earth's core-mantle boundary consists of a highly heterogeneous metal-oxide interface subjected to high temperatures, pressures, and additionally, to the presence of a temporally- and spatially-varying electrical field generated by the outer core dynamo. An understanding of the core-mantle boundary should include the nature of its electrical behavior, its electrically induced chemical partitioning, and any resultant core-mantle dynamic coupling. To this end, we have developed a method to measure the electrical behavior of metal-silicate interfaces at high pressures (15-25 kbar) and temperatures (1300-1400° C) in a piston-cylinder apparatus. Platinum electrical leads are placed at each end of the sample, which consists of a layer of iron and/or iron alloy below a layer of silicate. The sample is enclosed in a sintered MgO chamber which is then surrounded by a metal Faraday cage, allowing the sample to be electrically insulated from the AC field of the graphite heater. The platinum electric leads are threaded through the thermocouple tube and connected with an HP4284A LCR meter to measure AC impedance, or to a DC power supply to apply a field such that either the silicate or the metal end is the anode (+). AC impedance measurements performed in-situ on samples consisting of Fe, Fe-Ni-S, and a basalt-olivine mixture in series show that conductivity is strongly dependent on the electrical polarization of the silicate relative to the sulfide. When the silicate is positively charged (silicate is the anode) and when there is no applied charge, the probe-to-probe resistance displays semiconductor behavior, with conductivity ( ~10-2 S/cm) strongly thermally activated. However, when the electrical polarity is reversed, and the sulfide is the anode, the electrical conductivity between the two probes increases dramatically (to ~1 S/cm) over timescales of minutes. If the polarity is removed or reversed, the conductivity returns to its original values over similar timescales. A second set of experiments examined the behavior of iron-silicate interfaces subjected to electric fields of 1-10 V, applied for times ranging from several minutes to several days. The samples were quenched from high temperatures, mounted, and examined using both light and electron microscopy. When the iron/iron-sulfide end is charged positively (+1-2 V) with respect to the silicate, oxides form around the platinum electrode embedded within the iron metal, suggesting the reaction Fe->Fe+2+2e- occurs in the metal. When the electric field is reversed, the silicate and MgO surrounding the + electrode turns red, implying the reaction Fe+2\\rightarrowFe^{+3}+e^{-}$ occurs at the silicate (anode end) of the sample. The richness of electrical and electrically activated chemical behavior observed at metal-silicate interfaces may be relevant to the Earth's core mantle boundary.

The characterization of secondary lithium-ion battery degradation when operating complex, ultra-high power pulsed loads

NASA Astrophysics Data System (ADS)

Wong, Derek N.

The US Navy is actively developing all electric fleets, raising serious questions about what is required of onboard power supplies in order to properly power the ship's electrical systems. This is especially relevant when choosing a viable power source to drive high power propulsion and electric weapon systems in addition to the conventional loads deployed aboard these types of vessels. Especially when high pulsed power loads are supplied, the issue of maintaining power quality becomes important and increasingly complex. Conventionally, a vessel's electrical power is generated using gas turbine or diesel driven motor-generator sets that are very inefficient when they are used outside of their most efficient load condition. What this means is that if the generator is not being utilized continuously at its most efficient load capacity, the quality of the output power may also be effected and fall outside of the acceptable power quality limits imposed through military standards. As a solution to this potential problem, the Navy has proposed using electrochemical storage devices since they are able to buffer conventional generators when the load is operating below the generator's most efficient power level or able to efficiently augment a generator when the load is operating in excess of the generator's most efficient power rating. Specifically, the US Navy is interested in using commercial off-the-shelf (COTS) lithium-ion batteries within an intelligently controlled energy storage module that could act as either a prime power supply for on-board pulsed power systems or as a backup generator to other shipboard power systems. Due to the unique load profile of high-rate pulsed power systems, the implementation of lithium-ion batteries within these complex systems requires them to be operated at very high rates and the effects these things have on cell degradation has been an area of focus. There is very little published research into the effects that high power transient or pulsed loading has on the degradation mechanisms of secondary lithium-ion cells. Prior to performing this work, it was unclear if the implementation of lithium-ion batteries in highly transient load conditions at high rate would accelerate cell degradation mechanisms that have been previously considered as minor issues. This work has focused on answering these previously unanswered questions. In early experiments performed here, COTS lithium-iron-phosphate (LFP) cells were studied under high-rate, transient load conditions and it was found that their capacity fade deviated from the traditional linear behavior and exponentially declined until no charge could be accepted when recharge was attempted at high rate. These findings indicated that subjecting LFP chemistries to transient, high rate charge/discharge profiles induced rapid changes in the electrode/electrolyte interface that rendered the cells useless when high rate recharge was required. These findings suggested there was more phenomena to learn about how these cells degraded under high rate pulsed conditions before they are fielded in Naval applications. Therefore, the research presented here has been focused on understanding the degradation mechanisms that are unique to LFP cells when they are cycled under pulsed load profiles at high charge and discharge rates. In particular, the work has been focused on identifying major degradation reactions that occur by studying the surface chemistry of cycled electrode materials. Efforts have been performed to map the impedance evolution of both cathode and anode half cells, respectively, using a novel three electrode technique that was developed for this research. Using this technique, the progression of degradation has been mapped using analysis of differential capacitance spectrums. In both the three electrode EIS mapping and differential capacitance analysis that has been performed, electrical component models have been developed. The results presented will show that there are unique degradation mechanisms induced through high rate pulsed loading conditions that are not normally seen in low rate continuous cycling of LFP cells.

Study of VUV Generation by Coherent Resonant Frequency Mixing in Metal Vapors.

DTIC Science & Technology

1986-04-24

measuroments of coherent two- dye-laser oscillator -2 mplifier system designed for ex- photon aborption in lithium demonstrate that this periments t res(ona-nt...Harmonic Vacuum-Ultraviolet Generation in Metal Vapors," Phys. Rev. A 19, 1589 (1979). 2. ,.-C. Diels. E. W. Van Strvhand. and D. Gold , in Picosecond

Robust Pinhole-free Li3N Solid Electrolyte Grown from Molten Lithium

PubMed Central

2017-01-01

Lithium metal is the ultimate anode choice for high energy density rechargeable lithium batteries. However, it suffers from inferior electrochemical performance and safety issues due to its high reactivity and the growth of lithium dendrites. It has long been desired to develop a materials coating on Li metal, which is pinhole-free, mechanically robust without fracture during Li metal deposition and stripping, and chemically stable against Li metal and liquid electrolytes, all while maintaining adequate ionic conductivity. However, such an ideal material coating has yet to be found. Here we report a novel synthesis method by reacting clean molten lithium foil directly with pure nitrogen gas to generate instantaneously a pinhole-free and ionically conductive α-Li3N film directly bonded onto Li metal foil. The film consists of highly textured large Li3N grains (tens of μm) with (001) crystalline planes parallel to the Li metal surface. The bonding between textured grains is strong, resulting in a mechanically robust film which does not crack even when bent to a 0.8 cm curvature radius and is found to maintain pinhole-free coverage during Li metal deposition and stripping. The measured ionic conductivity is up to 5.2 × 10–4 S cm–1, sufficient for maintaining regular current densities for controllable film thicknesses ranging from 2 to 30 μm. This Li3N coating is chemically stable, isolating the reactive metallic lithium from liquid electrolyte, prevents continuous electrolyte consumption during battery cycling, and promotes dendrite-free uniform lithium plating/stripping underneath. We demonstrated Li|Li4Ti5O12 cells with stable and flat potential profiles for 500 cycles without capacity decay or an increase in potential hysteresis. PMID:29392181

Electrospun core-shell microfiber separator with thermal-triggered flame-retardant properties for lithium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Kai; Liu, Wei; Qiu, Yongcai

Although the energy densities of batteries continue to increase, safety problems (for example, fires and explosions) associated with the use of highly flammable liquid organic electrolytes remain a big issue, significantly hindering further practical applications of the next generation of high-energy batteries. We have fabricated a novel “smart” nonwoven electrospun separator with thermal-triggered flame-retardant properties for lithium-ion batteries. The encapsulation of a flame retardant inside a protective polymer shell has prevented direct dissolution of the retardant agent into the electrolyte, which would otherwise have negative effects on battery performance. Furthermore, during thermal runaway of the lithium-ion battery, the protective polymermore » shell would melt, triggered by the increased temperature, and the flame retardant would be released, thus effectively suppressing the combustion of the highly flammable electrolytes.« less

Rechargeable nickel-3D zinc batteries: An energy-dense, safer alternative to lithium-ion.

PubMed

Parker, Joseph F; Chervin, Christopher N; Pala, Irina R; Machler, Meinrad; Burz, Michael F; Long, Jeffrey W; Rolison, Debra R

2017-04-28

The next generation of high-performance batteries should include alternative chemistries that are inherently safer to operate than nonaqueous lithium-based batteries. Aqueous zinc-based batteries can answer that challenge because monolithic zinc sponge anodes can be cycled in nickel-zinc alkaline cells hundreds to thousands of times without undergoing passivation or macroscale dendrite formation. We demonstrate that the three-dimensional (3D) zinc form-factor elevates the performance of nickel-zinc alkaline cells in three fields of use: (i) >90% theoretical depth of discharge (DOD Zn ) in primary (single-use) cells, (ii) >100 high-rate cycles at 40% DOD Zn at lithium-ion-commensurate specific energy, and (iii) the tens of thousands of power-demanding duty cycles required for start-stop microhybrid vehicles. Copyright © 2017, American Association for the Advancement of Science.

Recent Developments of All-Solid-State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes.

PubMed

Xu, Ruochen; Zhang, Shengzhao; Wang, Xiuli; Xia, Yan; Xia, Xinhui; Wu, Jianbo; Gu, Changdong; Tu, Jiangping

2018-04-20

Due to the increasing demand of security and energy density, all-solid-state lithium ion batteries have become the promising next-generation energy storage devices to replace the traditional liquid batteries with flammable organic electrolytes. In this Minireview, we focus on the recent developments of sulfide inorganic electrolytes for all-solid-state batteries. The challenges of assembling bulk-type all-solid-state batteries for industrialization are discussed, including low ionic conductivity of the present sulfide electrolytes, high interfacial resistance and poor compatibility between electrolytes and electrodes. Many efforts have been focused on the solutions for these issues. Although some progresses have been achieved, it is still far away from practical application. The perspectives for future research on all-solid-state lithium ion batteries are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrospun core-shell microfiber separator with thermal-triggered flame-retardant properties for lithium-ion batteries

DOE PAGES

Liu, Kai; Liu, Wei; Qiu, Yongcai; ...

2017-01-13

Although the energy densities of batteries continue to increase, safety problems (for example, fires and explosions) associated with the use of highly flammable liquid organic electrolytes remain a big issue, significantly hindering further practical applications of the next generation of high-energy batteries. We have fabricated a novel “smart” nonwoven electrospun separator with thermal-triggered flame-retardant properties for lithium-ion batteries. The encapsulation of a flame retardant inside a protective polymer shell has prevented direct dissolution of the retardant agent into the electrolyte, which would otherwise have negative effects on battery performance. Furthermore, during thermal runaway of the lithium-ion battery, the protective polymermore » shell would melt, triggered by the increased temperature, and the flame retardant would be released, thus effectively suppressing the combustion of the highly flammable electrolytes.« less

Study of the response of a lithium yttrium borate scintillator based neutron rem counter by Monte Carlo radiation transport simulations

NASA Astrophysics Data System (ADS)

Sunil, C.; Tyagi, Mohit; Biju, K.; Shanbhag, A. A.; Bandyopadhyay, T.

2015-12-01

The scarcity and the high cost of 3He has spurred the use of various detectors for neutron monitoring. A new lithium yttrium borate scintillator developed in BARC has been studied for its use in a neutron rem counter. The scintillator is made of natural lithium and boron, and the yield of reaction products that will generate a signal in a real time detector has been studied by FLUKA Monte Carlo radiation transport code. A 2 cm lead introduced to enhance the gamma rejection shows no appreciable change in the shape of the fluence response or in the yield of reaction products. The fluence response when normalized at the average energy of an Am-Be neutron source shows promise of being used as rem counter.

Role of Amines in Thermal-Runaway-Mitigating Lithium-Ion Battery.

PubMed

Shi, Yang; Noelle, Daniel J; Wang, Meng; Le, Anh V; Yoon, Hyojung; Zhang, Minghao; Meng, Ying Shirley; Qiao, Yu

2016-11-16

Benzylamine (BA), dibenzylamine (DBA), and trihexylamine (THA) are investigated as thermal-runaway retardants (TRR) for lithium-ion batteries (LIBs). In a LIB, TRR is packaged separately and released when internal shorting happens, so as to suppress exothermic reactions and slow down temperature increase. THA is identified as the most efficient TRR. Upon nail penetration, 4 wt % THA can reduce the peak temperature by nearly 50%. The working mechanisms of the three amines are different: THA is highly wettable to the separator and immiscible with the electrolyte, and therefore, it blocks lithium-ion (Li + ) transport. BA and DBA decrease the ionic conductivity of electrolyte and increase the charge transfer resistance. All three amines react with charged electrodes; the reactions of DBA and THA do not have much influence on the overall heat generation, while the reaction of BA cannot be ignored.

Electrospun core-shell microfiber separator with thermal-triggered flame-retardant properties for lithium-ion batteries

PubMed Central

Liu, Kai; Liu, Wei; Qiu, Yongcai; Kong, Biao; Sun, Yongming; Chen, Zheng; Zhuo, Denys; Lin, Dingchang; Cui, Yi

2017-01-01

Although the energy densities of batteries continue to increase, safety problems (for example, fires and explosions) associated with the use of highly flammable liquid organic electrolytes remain a big issue, significantly hindering further practical applications of the next generation of high-energy batteries. We have fabricated a novel “smart” nonwoven electrospun separator with thermal-triggered flame-retardant properties for lithium-ion batteries. The encapsulation of a flame retardant inside a protective polymer shell has prevented direct dissolution of the retardant agent into the electrolyte, which would otherwise have negative effects on battery performance. During thermal runaway of the lithium-ion battery, the protective polymer shell would melt, triggered by the increased temperature, and the flame retardant would be released, thus effectively suppressing the combustion of the highly flammable electrolytes. PMID:28097221

Superior lithium storage performance using sequentially stacked MnO2/reduced graphene oxide composite electrodes.

PubMed

Kim, Sue Jin; Yun, Young Jun; Kim, Ki Woong; Chae, Changju; Jeong, Sunho; Kang, Yongku; Choi, Si-Young; Lee, Sun Sook; Choi, Sungho

2015-04-24

Hybrid nanostructures based on graphene and metal oxides hold great potential for use in high-performance electrode materials for next-generation lithium-ion batteries. Herein, a new strategy to fabricate sequentially stacked α-MnO2 /reduced graphene oxide composites driven by surface-charge-induced mutual electrostatic interactions is proposed. The resultant composite anode exhibits an excellent reversible charge/discharge capacity as high as 1100 mA h g(-1) without any traceable capacity fading, even after 100 cycles, which leads to a high rate capability electrode performance for lithium ion batteries. Thus, the proposed synthetic procedures guarantee a synergistic effect of multidimensional nanoscale media between one (metal oxide nanowire) and two dimensions (graphene sheet) for superior energy-storage electrodes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrospun core-shell microfiber separator with thermal-triggered flame-retardant properties for lithium-ion batteries.

PubMed

Liu, Kai; Liu, Wei; Qiu, Yongcai; Kong, Biao; Sun, Yongming; Chen, Zheng; Zhuo, Denys; Lin, Dingchang; Cui, Yi

2017-01-01

Although the energy densities of batteries continue to increase, safety problems (for example, fires and explosions) associated with the use of highly flammable liquid organic electrolytes remain a big issue, significantly hindering further practical applications of the next generation of high-energy batteries. We have fabricated a novel "smart" nonwoven electrospun separator with thermal-triggered flame-retardant properties for lithium-ion batteries. The encapsulation of a flame retardant inside a protective polymer shell has prevented direct dissolution of the retardant agent into the electrolyte, which would otherwise have negative effects on battery performance. During thermal runaway of the lithium-ion battery, the protective polymer shell would melt, triggered by the increased temperature, and the flame retardant would be released, thus effectively suppressing the combustion of the highly flammable electrolytes.

Hierarchically porous Li3VO4/C nanocomposite as an advanced anode material for high-performance lithium-ion capacitors

NASA Astrophysics Data System (ADS)

Xu, Xuena; Niu, Feier; Zhang, Dapeng; Chu, Chenxiao; Wang, Chunsheng; Yang, Jian; Qian, Yitai

2018-04-01

Lithium-ion capacitors, as a hybrid electrochemical energy storage device, realize high specific energy and power density within one device, thus attracting extensive attention. Here, hierarchically porous Li3VO4/C nanocomposite is prepared by a solvo-thermal reaction, followed with a post-annealing process. This composite has macropores at the center and mesopores in the wall, thus effectively promoting electrolyte penetration and structure stability upon cycling simultaneously. Compared to mesoporous Li3VO4, the enhanced rate capability and specific capacity of hierarchically porous Li3VO4/C indicate the synergistic effect of mesopores and macropores. Inspired by these results, this composite is coupled with mesoporous carbon (CMK-3) for lithium-ion capacitors, generating a specific energy density of 105 Wh kg-1 at a power density of 188 W kg-1. Even if the power density increases to 9.3 kW kg-1, the energy density still remains 62 Wh kg-1. All these results demonstrate the promising potential of hierarchically porous Li3VO4 in lithium ion capacitors.

Construction of nanostructures for selective lithium ion conduction using self-assembled molecular arrays in supramolecular solids

NASA Astrophysics Data System (ADS)

Moriya, Makoto

2017-12-01

In the development of innovative molecule-based materials, the identification of the structural features in supramolecular solids and the understanding of the correlation between structure and function are important factors. The author investigated the development of supramolecular solid electrolytes by constructing ion conduction paths using a supramolecular hierarchical structure in molecular crystals because the ion conduction path is an attractive key structure due to its ability to generate solid-state ion diffusivity. The obtained molecular crystals exhibited selective lithium ion diffusion via conduction paths consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and small molecules such as ether or amine compounds. In the present review, the correlation between the crystal structure and ion conductivity of the obtained molecular crystals is addressed based on the systematic structural control of the ionic conduction paths through the modification of the component molecules. The relationship between the crystal structure and ion conductivity of the molecular crystals provides a guideline for the development of solid electrolytes based on supramolecular solids exhibiting rapid and selective lithium ion conduction.

NASA Aerospace Flight Battery Program: Generic Safety, Handling and Qualification Guidelines for Lithium-Ion (Li-Ion) Batteries; Availability of Source Materials for Lithium-Ion (Li-Ion) Batteries; Maintaining Technical Communications Related to Aerospace Batteries (NASA Aerospace Battery Workshop). Volume 1, Part 1

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Brewer, Jeffrey C.; Bugga, Ratnakumar V.; Darcy, Eric C.; Jeevarajan, Judith A.; McKissock, Barbara I.; Schmitz, Paul C.

2010-01-01

This NASA Aerospace Flight Battery Systems Working Group was chartered within the NASA Engineering and Safety Center (NESC). The Battery Working Group was tasked to complete tasks and to propose proactive work to address battery related, agency-wide issues on an annual basis. In its first year of operation, this proactive program addressed various aspects of the validation and verification of aerospace battery systems for NASA missions. Studies were performed, issues were discussed and in many cases, test programs were executed to generate recommendations and guidelines to reduce risk associated with various aspects of implementing battery technology in the aerospace industry. This document contains Part 1 - Volume I: Generic Safety, Handling and Qualification Guidelines for Lithium-Ion (Li-Ion) Batteries, Availability of Source Materials for Lithium-Ion (Li-Ion) Batteries, and Maintaining Technical Communications Related to Aerospace Batteries (NASA Aerospace Battery Workshop).

First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution

DOE PAGES

Kamphaus, Ethan P.; Balbuena, Perla B.

2017-09-07

We present the Lithium-Sulfur battery is a promising next generation energy storage technology that could meet the demands of modern society with a theoretical specific energy near 2500 W h kg -1. However, this battery chemistry faces unique problems such as the parasitic polysulfide shuttle reaction which hinders battery performance severely. This shuttle phenomenon is caused by solubilities of intermediate reaction products in the electrolyte during the reduction chemistry of the battery. With molecular simulation and computational chemistry tools, we studied the thermodynamics, solvation structure, and dynamics of the long-chain lithium polysulfide species Li 2S 6 and Li 2S 8more » in dimethoxyethane and 1,3-dioxolane to gain a deeper fundamental understanding of this process. We determined the structure of the 1st solvation shell for Li + as well as those of Li 2S 6, Li 2S 8 closed and Li 2S 8 linear in pure solvents and solvents with extra Li + added. Finally, the lithium polysulfide species were found not to favor dissociation and would most likely exist as fully lithiated species in solution.« less

Superconcentrated electrolytes for a high-voltage lithium-ion battery

PubMed Central

Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro; Chiang, Ching Hua; Tateyama, Yoshitaka; Yamada, Atsuo

2016-01-01

Finding a viable electrolyte for next-generation 5 V-class lithium-ion batteries is of primary importance. A long-standing obstacle has been metal-ion dissolution at high voltages. The LiPF6 salt in conventional electrolytes is chemically unstable, which accelerates transition metal dissolution of the electrode material, yet beneficially suppresses oxidative dissolution of the aluminium current collector; replacing LiPF6 with more stable lithium salts may diminish transition metal dissolution but unfortunately encounters severe aluminium oxidation. Here we report an electrolyte design that can solve this dilemma. By mixing a stable lithium salt LiN(SO2F)2 with dimethyl carbonate solvent at extremely high concentrations, we obtain an unusual liquid showing a three-dimensional network of anions and solvent molecules that coordinate strongly to Li+ ions. This simple formulation of superconcentrated LiN(SO2F)2/dimethyl carbonate electrolyte inhibits the dissolution of both aluminium and transition metal at around 5 V, and realizes a high-voltage LiNi0.5Mn1.5O4/graphite battery that exhibits excellent cycling durability, high rate capability and enhanced safety. PMID:27354162

First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kamphaus, Ethan P.; Balbuena, Perla B.

We present the Lithium-Sulfur battery is a promising next generation energy storage technology that could meet the demands of modern society with a theoretical specific energy near 2500 W h kg -1. However, this battery chemistry faces unique problems such as the parasitic polysulfide shuttle reaction which hinders battery performance severely. This shuttle phenomenon is caused by solubilities of intermediate reaction products in the electrolyte during the reduction chemistry of the battery. With molecular simulation and computational chemistry tools, we studied the thermodynamics, solvation structure, and dynamics of the long-chain lithium polysulfide species Li 2S 6 and Li 2S 8more » in dimethoxyethane and 1,3-dioxolane to gain a deeper fundamental understanding of this process. We determined the structure of the 1st solvation shell for Li + as well as those of Li 2S 6, Li 2S 8 closed and Li 2S 8 linear in pure solvents and solvents with extra Li + added. Finally, the lithium polysulfide species were found not to favor dissociation and would most likely exist as fully lithiated species in solution.« less

Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}: Structural, spectroscopic and computational studies on a sorosilicate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kahlenberg, Volker, E-mail: volker.kahlenberg@uibk.ac.at; Brunello, Emanuele; Hejny, Clivia

2015-05-15

Synthesis experiments in the system Li{sub 2}O–CaO–SiO{sub 2} resulted in the formation of single-crystals of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}. Structural investigations were based on single-crystal diffraction. At ambient conditions the compound has the following basic crystallographic data: hexagonal symmetry, space group P6{sub 1}22, a=5.0961(2) Å, c=41.264(2) Å, V=928.07(6) Å{sup 3}, Z=6. Structure solution was performed using direct methods. The final least-squares refinement calculations converged at a residual of R(|F|)=0.0260. From a structural point the lithium calcium silicate belongs to the group of pyrosilicates containing [Si{sub 2}O{sub 7}]-groups. Additional lithium and calcium cations are incorporated between the silicate dimers andmore » are coordinated by four and six nearest oxygen neighbours, respectively. Each [LiO{sub 4}]-tetrahedron shares two common corners with directly neighboring tetrahedra forming zweier single-chains which are running parallel to 〈1 0 0〉 in z-levels defined by the presence of the 6{sub 1}{sup [0} {sup 0} {sup 1]}-screw axes. From the corner-sharing [LiO{sub 4}]- and [SiO{sub 4}]-moieties a three dimensional framework can be constructed. An interesting feature of this framework is the presence of an O{sup [3]}-type bridging oxygen linking three tetrahedra (one [LiO{sub 4}]- and two [SiO{sub 4}]-units). Structural similarities with other silicates are discussed in detail. The high-temperature behavior of the Si–O, Ca–O and Li–O bond distances in Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} was investigated by in{sub -}situ single-crystal X-ray diffraction in the range between 65 and 700 °C. From the evolution of the lattice parameters, the thermal expansion tensor α{sub ij} has been determined. The structural characterization has been supplemented by micro-Raman spectroscopy. Interpretation of the spectroscopic data including the allocation of the bands to certain vibrational species has been aided by DFT-calculations. - Graphical abstract: Framework of [SiO{sub 4}]- and [LiO{sub 4}]-tetrahedra in the crystal structure of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}. - Highlights: • We report the crystal structure of the sorosilicate Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} at ambient conditions. • The thermal expansion tensor as well as the evolution of the structure between 25 and 700 °C was studied. • A topological analysis of the tetrahedral framework based on [SiO{sub 4}]- and [LiO{sub 4}]-units is presented. • The crystal structure of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} is discussed with respect to related compounds. • Interpretation of the Raman spectra of the crystals has been aided by DFT-calculations.« less

Processes Influencing the Timing and Volume of Eruptions From the Youngest Supervolcano on Earth

NASA Astrophysics Data System (ADS)

Wilson, C. J. N.; Barker, S. J.; Morgan, D. J.; Rowland, J. V.; Schipper, I.

2015-12-01

In their stratigraphic records, silicic caldera volcanoes display wide ranges of eruptive styles and volumes. However, relationships between frequency and magnitude are often complex, and the forecasting of future activity is inherently problematic. Taupo volcano, New Zealand, provides a unique opportunity to investigate eruptive histories from a hyperactive, large silicic magmatic system with eruptive volumes that span 3-4 orders of magnitude, and show no clear relationships with the repose period. Taupo hosted the world's most recent supereruption at 25.4 ka, which discharged 530 km3 of magma in the episodic 10-phase Oruanui event. Only 5 kyr later, Taupo revived, with 3 dacitic eruptions from 21.5-17 ka and 25 rhyolite eruptions from 12-1.7 ka. Here we use trends in whole rock, glass and mineral chemistry to show how the magma system reestablished following the Oruanui event, and to consider what processes influence the state of the modern volcano. The post-Oruanui dacites reflect the first products of the rebuilding silicic magma system, as most of the Oruanui mush was reconfigured or significantly modified in composition following thermal fluxing accompanying post-caldera collapse readjustment. Compositional variations within the younger rhyolites at <12 ka reflect fine-scale temporal changes in mineral phase stability, closely linked to the development, stabilization and maturation of a new silicic mush system. For the most recent eruptions, the system underwent destabilization, resulting in increased volumes of melt extraction from the silicic mush. Orthopyroxene Fe-Mg diffusion timescales indicate that the onset of rapid heating and priming of the silicic mush occurred <100 years prior to the <2.15 ka eruptions, with subsequent melt accumulation occurring in only decades. The largest post-Oruanui eruption at 232 AD culminated from elevated mafic magma supply to the silicic mush pile, rapid melt accumulation and high differential tectonic stress build up, leading to one of the largest and most violent Holocene eruptions globally. The latest eruptions of Taupo highlight the multiple controls on the timing of eruptions, and demonstrate how the magmatic system can rapidly change behavior to generate large eruptible melt bodies on timescales of direct relevance to humans and monitoring initiatives.

The acid and alkalinity budgets of weathering in the Andes-Amazon system: Insights into the erosional control of global biogeochemical cycles

NASA Astrophysics Data System (ADS)

Torres, Mark A.; West, A. Joshua; Clark, Kathryn E.; Paris, Guillaume; Bouchez, Julien; Ponton, Camilo; Feakins, Sarah J.; Galy, Valier; Adkins, Jess F.

2016-09-01

The correlation between chemical weathering fluxes and denudation rates suggests that tectonic activity can force variations in atmospheric pCO2 by modulating weathering fluxes. However, the effect of weathering on pCO2 is not solely determined by the total mass flux. Instead, the effect of weathering on pCO2 also depends upon the balance between 1) alkalinity generation by carbonate and silicate mineral dissolution and 2) sulfuric acid generation by the oxidation of sulfide minerals. In this study, we explore how the balance between acid and alkalinity generation varies with tectonic uplift to better understand the links between tectonics and the long-term carbon cycle. To trace weathering reactions across the transition from the Peruvian Andes to the Amazonian foreland basin, we measured a suite of elemental concentrations (Na, K, Ca, Mg, Sr, Si, Li, SO4, and Cl) and isotopic ratios (87Sr/86Sr and δ34S) on both dissolved and solid phase samples. Using an inverse model, we quantitatively link systematic changes in solute geochemistry with elevation to downstream declines in sulfuric acid weathering as well as the proportion of cations sourced from silicates. With a new carbonate-system framework, we show that weathering in the Andes Mountains is a CO2 source whereas foreland weathering is a CO2 sink. These results are consistent with the theoretical expectation that the ratio of sulfide oxidation to silicate weathering increases with increasing erosion. Altogether, our results suggest that the effect of tectonically-enhanced weathering on atmospheric pCO2 is strongly modulated by sulfide mineral oxidation.

Corrosion Performance of New Generation Aluminum-Lithium Alloys for Aerospace Applications

NASA Astrophysics Data System (ADS)

Moran, James P.; Bovard, Francine S.; Chrzan, James D.; Vandenburgh, Peter

Over the past several years, a new generation of aluminum-lithium alloys has been developed. These alloys are characterized by excellent strength, low density, and high modulus of elasticity and are therefore of interest for lightweight structural materials applications particularly for construction of current and future aircraft. These new alloys have also demonstrated significant improvements in corrosion resistance when compared with the legacy and incumbent alloys. This paper documents the superior corrosion resistance of the current commercial tempers of these materials and also discusses the corrosion performance as a function of the degree of artificial aging. Results from laboratory corrosion tests are compared with results from exposures in a seacoast atmosphere to assess the predictive capability of the laboratory tests. The correlations that have been developed between the laboratory tests and the seacoast exposures provide confidence that a set of available methods can provide an accurate assessment of the corrosion performance of this new generation of alloys.

Inverted battery design as ion generator for interfacing with biosystems

DOE PAGES

Wang, Chengwei; Fu, Kun; Dai, Jiaqi; ...

2017-07-24

In a lithium-ion battery, electrons are released from the anode and go through an external electronic circuit to power devices, while ions simultaneously transfer through internal ionic media to meet with electrons at the cathode. Inspired by the fundamental electrochemistry of the lithium-ion battery, we envision a cell that can generate a current of ions instead of electrons, so that ions can be used for potential applications in biosystems. Based on this concept, we report an ‘electron battery’ configuration in which ions travel through an external circuit to interact with the intended biosystem whereas electrons are transported internally. As amore » proof-of-concept, we demonstrate the application of the electron battery by stimulating a monolayer of cultured cells, which fluoresces a calcium ion wave at a controlled ionic current. Electron batteries with the capability to generate a tunable ionic current could pave the way towards precise ion-system control in a broad range of biological applications« less

Inverted battery design as ion generator for interfacing with biosystems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chengwei; Fu, Kun; Dai, Jiaqi

In a lithium-ion battery, electrons are released from the anode and go through an external electronic circuit to power devices, while ions simultaneously transfer through internal ionic media to meet with electrons at the cathode. Inspired by the fundamental electrochemistry of the lithium-ion battery, we envision a cell that can generate a current of ions instead of electrons, so that ions can be used for potential applications in biosystems. Based on this concept, we report an ‘electron battery’ configuration in which ions travel through an external circuit to interact with the intended biosystem whereas electrons are transported internally. As amore » proof-of-concept, we demonstrate the application of the electron battery by stimulating a monolayer of cultured cells, which fluoresces a calcium ion wave at a controlled ionic current. Electron batteries with the capability to generate a tunable ionic current could pave the way towards precise ion-system control in a broad range of biological applications« less

Tin-based anode materials with well-designed architectures for next-generation lithium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Lehao; Xie, Fan; Lyu, Jing; Zhao, Tingkai; Li, Tiehu; Choi, Bong Gill

2016-07-01

Tin (Sn) has long been considered to be a promising replacement anode material for graphite in next-generation lithium-ion batteries (LIBs), because of its attractive comprehensive advantages of high gravimetric/volumetric capacities, environmental benignity, low cost, high safety, etc. However, Sn-based anodes suffer from severe capacity fading resulting mainly from their large volume expansions/contractions during lithiation/delithiation and subsequent pulverization, coalescence, delamination from current collectors, and poor Li+/electron transport. To circumvent these issues, a number of extraordinary architectures from nanostructures to anchored, layered/sandwich, core-shell, porous and even integrated structures have been exquisitely constructed to enhance the cycling performance. To cater for the rapid development of Sn-based anodes, we summarize the advances made in structural design principles, fabrication methods, morphological features and battery performance with focus on material structures. In addition, we identify the associated challenges and problems presented by recently-developed anodes and offer suggestions and perspectives for facilitating their practical implementations in next-generation LIBs.

Inverted battery design as ion generator for interfacing with biosystems

PubMed Central

Wang, Chengwei; Fu, Kun (Kelvin); Dai, Jiaqi; Lacey, Steven D.; Yao, Yonggang; Pastel, Glenn; Xu, Lisha; Zhang, Jianhua; Hu, Liangbing

2017-01-01

In a lithium-ion battery, electrons are released from the anode and go through an external electronic circuit to power devices, while ions simultaneously transfer through internal ionic media to meet with electrons at the cathode. Inspired by the fundamental electrochemistry of the lithium-ion battery, we envision a cell that can generate a current of ions instead of electrons, so that ions can be used for potential applications in biosystems. Based on this concept, we report an ‘electron battery’ configuration in which ions travel through an external circuit to interact with the intended biosystem whereas electrons are transported internally. As a proof-of-concept, we demonstrate the application of the electron battery by stimulating a monolayer of cultured cells, which fluoresces a calcium ion wave at a controlled ionic current. Electron batteries with the capability to generate a tunable ionic current could pave the way towards precise ion-system control in a broad range of biological applications. PMID:28737174

Spectral characterization and white light generation by yttrium silicate nanopowders undoped and doped with Ytterbium(III) at different concentrations when excited by a laser diode at 975 nm

NASA Astrophysics Data System (ADS)

Cinkaya, Hatun; Eryurek, Gonul; Bilir, Gokhan; Collins, John; Di Bartolo, Baldassare

2017-01-01

We have studied nanophosphors of yttrium silicate (YSO) undoped and doped with different concentration of ytterbium (Yb3+) synthesized by using the sol-gel method. Structural and luminescence properties of the nanophosphors were studied experimentally by using different analytical techniques. For the structural analysis, we performed X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and Energy Dispersive X-ray Spectrometry (EDS) measurements. Upconversion (UC) and the white light (WL) emission properties were investigated by using the near infrared cw laser excitation of 975 nm. The spectral properties have been found to depend on several physical parameters.

Developing New Electrolytes for Advanced Li-ion Batteries

NASA Astrophysics Data System (ADS)

McOwen, Dennis Wayne

The use of renewable energy sources is on the rise, as new energy generating technologies continue to become more efficient and economical. Furthermore, the advantages of an energy infrastructure which relies more on sustainable and renewable energy sources are becoming increasingly apparent. The most readily available of these renewable energy sources, wind and solar energy in particular, are naturally intermittent. Thus, to enable the continued expansion and widespread adoption of renewable energy generating technology, a cost-effective energy storage system is essential. Additionally, the market for electric/hybrid electric vehicles, which both require efficient energy storage, continues to grow as more consumers seek to reduce their consumption of gasoline. These vehicles, however, remain quite expensive, due primarily to costs associated with storing the electrical energy. High-voltage and thermally stable Li-ion battery technology is a promising solution for both grid-level and electric vehicle energy storage. Current limitations in materials, however, limit the energy density and safe operating temperature window of the battery. Specifically, the state-of-the-art electrolyte used in Li-ion batteries is not compatible with recently developed high-voltage positive electrodes, which are one of the most effectual ways of increasing the energy density. The electrolyte is also thermally unstable above 50 °C, and prone to thermal runaway reaction if exposed to prolonged heating. The lithium salt used in such electrolytes, LiPF6, is a primary contributor to both of these issues. Unfortunately, an improved lithium salt which meets the myriad property requirements for Li-ion battery electrolytes has eluded researchers for decades. In this study, a renewed effort to find such a lithium salt was begun, using a recently developed methodology to rapidly screen for desirable properties. Four new lithium salts and one relatively new but uncharacterized lithium salt were synthesized for this investigation: dilithium 1,2,5-thiadiazolidine-3,4-dione-1,1-dioxide (Li2TDD), lithium ethyl N-trifluoroacetylcarbamate (LiETAC), lithium hexafluoroisopropoxide (LiHFI), lithium pentafluorophenolate (LiPFPO), and lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI). Using crystalline solvate structure analysis and electrolyte solvation numbers, each of these lithium salts were compared to more well-characterized lithium salts, such as LiPF6 and LiBF4. From this study, links between anion structural characteristics and the anion...Li+ cation interactions (i.e., ionic association strength) were made. From the screening of the five lithium salts that were synthesized, LiTDI was determined to be a promising candidate for Li-ion battery electrolytes. Further characterization of carbonate- and mixed carbonate-LiTDI electrolytes (e.g., ionic conductivity) confirmed this to be the case. Coin cells containing LiTDI or LiPF6 electrolytes showed that cells with either electrolyte could deliver nearly identical power density at 25 °C. Additionally, thermogravimetric analysis (TGA) and NMR suggested that the LiTDI salt and carbonate-LiTDI electrolytes are thermally stable up to at least 60 °C. Further supporting this finding, coin cells cycled at 60 °C with LiPF6 lost significantly more capacity than those with LiTDI. Therefore, LiTDI is a prime candidate for the complete replacement of LiPF6 to significantly increase Li-ion battery tolerance to heat, improving the safety characteristics. In addition to searching for new lithium salts, the effect of lithium salt concentration on electrolyte physicochemical properties was investigated. This radically different approach to modifying electrolyte properties determined that amorphous, highly concentrated carbonate-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolytes have drastically different behavior than more dilute electrolytes. For example, the thermal stability and anodic stability vs. a Pt electrode of the concentrated electrolytes are significantly higher. Most striking, however, was the suppression of Al corrosion by the concentrated carbonate-LiTFSI electrolytes, despite the fact that Al corrosion of more dilute carbonate-LiTFSI electrolytes has consistently been attributed to the TFSI- anion in the literature. These results, explained by crystalline solvate analysis, Raman spectroscopy, and molecular dynamics simulations, could change the way Li-ion battery electrolytes are designed.

Compatibility of stainless steels and lithiated ceramics with beryllium

NASA Astrophysics Data System (ADS)

Flament, T.; Fauvet, P.; Sannier, J.

1988-07-01

The introduction of beryllium as a neutron multiplier in ceramic blankets of thermonuclear fusion reactors may give rise to the following compatibility problems: (i) oxidation of Be by ceramics (lithium aluminate and silicates) or by water vapour; (ii) interaction between beryllium and austenitic and martensitic steels. The studies were done in contact tests under vacuum and in tests under wet sweeping helium. The contact tests under vacuum have revealed that the interaction of beryllium with ceramics seems to be low up to 700°C, the interaction of beryllium with steels is significant and is characterized by the formation of a diffusion layer and of a brittle Be-Fe-Ni compound. With type 316 L austenitic steel, this interaction appears quite large at 600°C whereas it is noticeable only at 700°C with martensitic steels. The experiments carried out with sweeping wet helium at 600°C have evidenced a slight oxidation of beryllium due to water vapour which can be enhanced in the front of uncompletely dehydrated ceramics.

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

NASA Technical Reports Server (NTRS)

Ray, C. S.; Zhang, T.; Reis, S. T.; Brow, R. K.

2006-01-01

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

Lithium-free processing of silk fibroin.

PubMed

Zheng, Zhaozhu; Guo, Shaozhe; Liu, Yawen; Wu, Jianbing; Li, Gang; Liu, Meng; Wang, Xiaoqin; Kaplan, David

2016-09-01

Silk fibroin protein was purified from Bombyx mori silkworm cocoons using a novel dialysis strategy to avoid fibroin aggregation and pre-mature formation of β-sheets. The degummed silk fibers were dissolved in Ajisawa's reagent, a mixture of CaCl2-EtOH-H2O, that is less expensive than lithium bromide. The dissolved solutions were dialyzed against either water or urea solution with a stepwise decrease in concentration. When the steps of 4 M-2 M-1 M-0 M urea (referred to as silk-TS-4210) were adopted, the purified silk fibroin had smaller aggregates (<10 nm), similar average molecular weight (225 kDa) and a lower content of β-sheet (∼15%) compared to the sample processing methods (silk-TS-210, 10, 0) studied here. This outcome was close to the fibroin purified by the lithium bromide (silk-Li-0) method. Polyvinyl alcohol-emulsified silk microspheres generated using the purified solution had a similar size distribution and morphology when compared to lithium bromide dissolved solutions, while glycerol-blended silk films showed different mechanical properties. The silk-Li-0 generated films with the highest breaking strength (5.7 MPa ± 0.3) while the silk-TS-4210 had the highest extension at break (215.1% ± 12.5). The films prepared from silk-TS-4210 were cytocompatible to support the adhesion and proliferation of human mesenchymal stem cells, with improvements compared to the other samples likely due to the porous morphology of these films. © The Author(s) 2016.

Interfacial behavior of polymer electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerr, John; Kerr, John B.; Han, Yong Bong

2003-06-03

Evidence is presented concerning the effect of surfaces on the segmental motion of PEO-based polymer electrolytes in lithium batteries. For dry systems with no moisture the effect of surfaces of nano-particle fillers is to inhibit the segmental motion and to reduce the lithium ion transport. These effects also occur at the surfaces in composite electrodes that contain considerable quantities of carbon black nano-particles for electronic connection. The problem of reduced polymer mobility is compounded by the generation of salt concentration gradients within the composite electrode. Highly concentrated polymer electrolytes have reduced transport properties due to the increased ionic cross-linking. Combinedmore » with the interfacial interactions this leads to the generation of low mobility electrolyte layers within the electrode and to loss of capacity and power capability. It is shown that even with planar lithium metal electrodes the concentration gradients can significantly impact the interfacial impedance. The interfacial impedance of lithium/PEO-LiTFSI cells varies depending upon the time elapsed since current was turned off after polarization. The behavior is consistent with relaxation of the salt concentration gradients and indicates that a portion of the interfacial impedance usually attributed to the SEI layer is due to concentrated salt solutions next to the electrode surfaces that are very resistive. These resistive layers may undergo actual phase changes in a non-uniform manner and the possible role of the reduced mobility polymer layers in dendrite initiation and growth is also explored. It is concluded that PEO and ethylene oxide-based polymers are less than ideal with respect to this interfacial behavior.« less

An intense lithium ion beam source using vacuum baking and discharge cleaning techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moschella, J.J.; Kusse, B.R.; Longfellow, J.P.

We have developed a high-purity, intense, lithium ion beam source which operates at 500 kV and 120 A/cm{sup 2} with pulse widths of 125 ns full width half maximum. The beams were generated using a lithium chloride anode in planar magnetically insulated geometry. We have found that the combination of vacuum baking of the anode at 250 {degree}C followed by the application of 100 W of pure argon, steady-state, glow discharge cleaning reduced the impurity concentration in the beam to approximately 10% (components other than chlorine or lithium were considered impurities). Although the impurities were low, the concentration of chlorinemore » in the 1+ and 2+ charge states was significant ({similar to}25%). The remaining 65% of the beam consisted of Li{sup +} ions. Without the special cleaning process, over half the beam particles were impurities. It was determined that these impurities entered the beam at the anode surface but came originally from material in the vacuum chamber. After the cleaning process, recontamination was observed to occur in approximately 6 min. This long recontamination time, which was much greater than the expected monolayer formation time, was attributed to the elevated temperature of the anode. We also compared the electrical characteristics of the beams produced by LiCl anodes to those generated by a standard polyethylene proton source. In contrast to the polyethylene anode, the LiCl source exhibited a higher impedance, produced beams of lower ion current efficiency and had longer turn on times.« less

Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

PubMed

Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

2013-05-21

Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of batteries, the microstructure of the coating layers and the mechanism of action are not fully understood. Therefore, researchers will need to further investigate the surface coating strategy during the development of new lithium ion batteries.

Online differentiation of mineral phase in aerosol particles by ion formation mechanism using a LAAP-TOF single-particle mass spectrometer

NASA Astrophysics Data System (ADS)

Marsden, Nicholas A.; Flynn, Michael J.; Allan, James D.; Coe, Hugh

2018-01-01

Mineralogy of silicate mineral dust has a strong influence on climate and ecosystems due to variation in physiochemical properties that result from differences in composition and crystal structure (mineral phase). Traditional offline methods of analysing mineral phase are labour intensive and the temporal resolution of the data is much longer than many atmospheric processes. Single-particle mass spectrometry (SPMS) is an established technique for the online size-resolved measurement of particle composition by laser desorption ionisation (LDI) followed by time-of-flight mass spectrometry (TOF-MS). Although non-quantitative, the technique is able to identify the presence of silicate minerals in airborne dust particles from markers of alkali metals and silicate molecular ions in the mass spectra. However, the differentiation of mineral phase in silicate particles by traditional mass spectral peak area measurements is not possible. This is because instrument function and matrix effects in the ionisation process result in variations in instrument response that are greater than the differences in composition between common mineral phases.In this study, we introduce a novel technique that enables the differentiation of mineral phase in silicate mineral particles by ion formation mechanism measured from subtle changes in ion arrival times at the TOF-MS detector. Using a combination of peak area and peak centroid measurements, we show that the arrangement of the interstitial alkali metals in the crystal structure, an important property in silicate mineralogy, influences the ion arrival times of elemental and molecular ion species in the negative ion mass spectra. A classification scheme is presented that allowed for the differentiation of illite-smectite, kaolinite and feldspar minerals on a single-particle basis. Online analysis of mineral dust aerosol generated from clay mineral standards produced mineral fractions that are in agreement with bulk measurements reported by traditional XRD (X-ray diffraction) analysis.

Chemistry and petrography of calcite in the KTB pilot borehole, Bavarian Oberpfalz, Germany

USGS Publications Warehouse

Komor, S.C.

1995-01-01

The KTB pilot borehole in northeast Bavaria, Germany, penetrates 4000 m of gneiss, amphibolite, and subordinate calc-silicate, lamprophyre and metagabbro. There are three types of calcite in the drilled section: 1) metamorphic calcite in calc-silicate and marble; 2) crack-filling calcite in all lithologies; and 3) replacement calcite in altered minerals. Crack-filling and replacement calcite postdate metamorphic calcite. Multiple calcite generations in individual cracks suggest that different generations of water repeatedly flowed through the same cracks. Crack-filling mineral assemblages that include calcite originally formed at temperatures of 150-350??C. Presently, crack-filling calcite is in chemical and isotopic equilibrium with saline to brackish water in the borehole at temperatures of ???120??C. The saline to brackish water contains a significant proportion of meteoric water. Re-equilibration of crack-filling calcite to lower temperatures means that calcite chemistry tells us little about water-rock interactions in the crystal section of temperatures higher than ~120??C. -from Author

Integrated source of tunable nonmaximally mode-entangled photons in a domain-engineered lithium niobate waveguide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ming, Yang; Wu, Zi-jian; Xu, Fei, E-mail: feixu@nju.edu.cn

The nonmaximally entangled state is a special kind of entangled state, which has important applications in quantum information processing. It has been generated in quantum circuits based on bulk optical elements. However, corresponding schemes in integrated quantum circuits have been rarely considered. In this Letter, we propose an effective solution for this problem. An electro-optically tunable nonmaximally mode-entangled photon state is generated in an on-chip domain-engineered lithium niobate (LN) waveguide. Spontaneous parametric down-conversion and electro-optic interaction are effectively combined through suitable domain design to transform the entangled state into our desired formation. Moreover, this is a flexible approach to entanglementmore » architectures. Other kinds of reconfigurable entanglements are also achievable through this method. LN provides a very promising platform for future quantum circuit integration.« less

A pre-heating method based on sinusoidal alternating current for lithium-ion battery

NASA Astrophysics Data System (ADS)

Fan, Wentao; Sun, Fengchun; Guo, Shanshan

2018-04-01

In this paper, a method of low temperature pre-heating of sinusoidal alternating current (SAC) is proposed. Generally, the lower the frequency of the AC current, the higher the heat generation rate. Yet at low frequency, there is a risk of lithium-ion deposition during the half cycle of charging. This study develops a temperature-adaptive, deposition-free AC pre-heating method. a equivalent electric circuit(EEC) model is established to predict the heat generation rate and temperature status, whose parameters are calibrated from the EIS impedance measurements. The effects of current frequency and amplitude on the heating effect are investigated respectively. A multistep temperature-adaptive amplitude strategy is proposed and the cell can be heated from -20°C to 5°C within 509s at 100Hz frequency with this method.

Equilibrium lithium isotope fractionation in Li-rich minerals

NASA Astrophysics Data System (ADS)

Liu, S.; Li, Y.; Liu, J.

2017-12-01

Lithium is the lightest alkali metal, and only exhibits +1 valence state in minerals. It is widely distributed on the Earth, and usually substitutes for Mg in silicate minerals. Li has two stable isotopes, 6Li and 7Li, with the relative abundances of 7.52% and 92.48%, respectively. The large mass difference between 6Li and 7Li could induce significant isotope fractionation in minerals. Li isotopes can provide an important geochemical tracer for mantle processes. However, the fractionation factors for Li in most minerals remain poorly known, which makes the geochemical implications of Li isotope fractionations in minerals difficult to assess. Here, we try to use the vibrational frequencies obtained by the first-principles methods based on density-functional theory to calculate the Li isotope fractionation parameters for amblygonite (LiAlPO4F), bikitaite (LiSi2AlO7H2), eucryptite (LiAlSiO4), lithiophilite (LiMnPO4), lithiophosphate (Li3PO4), montebrasite (LiAlPO5H), and spodumene (LiAlSi2O6) in the temperature range of 0-1200 ºC. For forsterite (Mg2SiO4) and diopside (CaMgSi2O6) in which Li takes the place of Mg, the equilibrium Li isotope fractionation between them also be studied. Our preliminary calculations show that the coordination number of Li seems to play an important role in controlling Li isotope fractionation in these minerals, and concentration of Li in forsterite and diopside seems to have great effects on Li isotope fractionation factors of them.

[Application of simultaneous determination of inorganic ionic species by advanced ion chromatography for water quality monitoring of river water and wastewater].

PubMed

Nakatani, Nobutake; Kozaki, Daisuke; Tanaka, Kazuhiko

2012-04-01

In this study, our recent work on advanced ion chromatographic methods for the simultaneous determination of inorganic ionic species such as common anions (SO4(2-), Cl(-) and NO3(-)) and cations (Na+, NH4+, K+, Mg2+, and Ca2+), nutrients (phosphate and silicate) and hydrogen ion/alkalinity are summarized first. Then, the applications using these methods for monitoring environmental water quality are also presented. For the determination of common anions and cations with nutrients, the separation was successfully performed by a polymethacrylate-based weakly acidic cation-exchange column of TSKgel Super IC-A/C (Tosoh, 150 mm x 6.0 mm i. d.) and a mixture solution of 100 mmol/L ascorbic acid and 4 mmol/L 18-crown-6 as acidic eluent with dual detection of conductivity and spectrophotometry. For the determination of hydrogen ion/alkalinity, the separation was conducted by TSKgel ODS-100Z column (Tosoh, 150 mm x 4.5 mm i. d.) modified with lithium dodecylsulfate and an eluent of 40 mmol/L LiCl/0.1 mmol/L lithium dodecylsulfate/0.05 mmol/L H2SO4 with conductivity detector. The differences of ion concentration between untreated and treated wastewater showed the variation of ionic species during biological treatment process in a sewage treatment plant. Occurrence and distribution of water-quality conditions were related to the bioavailability and human activity in watershed. From these results, our advanced ion chromatographic methods have contributed significantly for water quality monitoring of environmental waters.

The effect of sodium chloride on the dissolution of calcium silicate hydrate gels.

PubMed

Hill, J; Harris, A W; Manning, M; Chambers, A; Swanton, S W

2006-01-01

The use of cement based materials will be widespread in the long-term management of radioactive materials in the United Kingdom. One of the applications could be the Nirex reference vault backfill (NRVB) as an engineered barrier within a deep geological repository. NRVB confers alkaline conditions, which would provide a robust chemical barrier through the control of the solubility of some key radionuclides, enhanced sorption and minimised corrosion of steel containers. An understanding of the dissolution of C-S-H gels in cement under the appropriate conditions (e.g., saline groundwaters) is necessary to demonstrate the expected evolution of the chemistry over time and to provide sufficient cement to buffer the porewater conditions for the required time. A programme of experimental work has been undertaken to investigate C-S-H gel dissolution behaviour in sodium chloride solutions and the effect of calcium/silicon ratio (C/S), temperature and cation type on this behaviour. Reductions in calcium concentration and pH values were observed with samples equilibrated at 45 degrees C compared to those prepared at 25 degrees C. The effect of salt cation type on salt-concentration dependence of the dissolution of C-S-H gels was investigated by the addition of lithium or potassium chloride in place of sodium chloride for gels with a C/S of 1.0 and 1.8. With a C/S of 1.0, similar increases in dissolved calcium concentration with increasing ionic strength were recorded for the different salts. However, at a C/S of 1.8, anomalously high calcium concentrations were observed in the presence of lithium.

The Sensitive Infrared Signal Detection by Sum Frequency Generation

NASA Technical Reports Server (NTRS)

Wong, Teh-Hwa; Yu, Jirong; Bai, Yingxin

2013-01-01

An up-conversion device that converts 2.05-micron light to 700 nm signal by sum frequency generation using a periodically poled lithium niobate crystal is demonstrated. The achieved 92% up-conversion efficiency paves the path to detect extremely weak 2.05-micron signal with well established silicon avalanche photodiode detector for sensitive lidar applications.

Next Generation Anodes for Lithium-Ion Batteries: Thermodynamic Understanding and Abuse Performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fenton, Kyle R.; Allcorn, Eric; Nagasubramanian, Ganesan

The objectives of this report are as follows: elucidate degradation mechanisms, decomposition products, and abuse response for next generation silicon based anodes; and Understand the contribution of various materials properties and cell build parameters towards thermal runaway enthalpies. Quantify the contributions from particle size, composition, state of charge (SOC), electrolyte to active materials ratio, etc.

Power and thermal characterization of a lithium-ion battery pack for hybrid-electric vehicles

NASA Astrophysics Data System (ADS)

Smith, Kandler; Wang, Chao-Yang

A 1D electrochemical, lumped thermal model is used to explore pulse power limitations and thermal behavior of a 6 Ah, 72 cell, 276 V nominal Li-ion hybrid-electric vehicle (HEV) battery pack. Depleted/saturated active material Li surface concentrations in the negative/positive electrodes consistently cause end of high-rate (∼25 C) pulse discharge at the 2.7 V cell -1 minimum limit, indicating solid-state diffusion is the limiting mechanism. The 3.9 V cell -1 maximum limit, meant to protect the negative electrode from lithium deposition side reaction during charge, is overly conservative for high-rate (∼15 C) pulse charges initiated from states-of-charge (SOCs) less than 100%. Two-second maximum pulse charge rate from the 50% SOC initial condition can be increased by as much as 50% without risk of lithium deposition. Controlled to minimum/maximum voltage limits, the pack meets partnership for next generation vehicles (PNGV) power assist mode pulse power goals (at operating temperatures >16 °C), but falls short of the available energy goal. In a vehicle simulation, the pack generates heat at a 320 W rate on a US06 driving cycle at 25 °C, with more heat generated at lower temperatures. Less aggressive FUDS and HWFET cycles generate 6-12 times less heat. Contact resistance ohmic heating dominates all other mechanisms, followed by electrolyte phase ohmic heating. Reaction and electronic phase ohmic heats are negligible. A convective heat transfer coefficient of h = 10.1 W m -2 K -1 maintains cell temperature at or below the 52 °C PNGV operating limit under aggressive US06 driving.

Mechanical and electrochemical response of a LiCoO 2 cathode using reconstructed microstructures

DOE PAGES

Mendoza, Hector; Roberts, Scott Alan; Brunini, Victor; ...

2016-01-01

As LiCoO 2 cathodes are charged, delithiation of the LiCoO 2 active material leads to an increase in the lattice spacing, causing swelling of the particles. When these particles are packed into a bicontinuous, percolated network, as is the case in a battery electrode, this swelling leads to the generation of significant mechanical stress. In this study we performed coupled electrochemical-mechanical simulations of the charging of a LiCoO 2 cathode in order to elucidate the mechanisms of stress generation and the effect of charge rate and microstructure on these stresses. Energy dispersive spectroscopy combined with scanning electron microscopy imaging wasmore » used to create 3D reconstructions of a LiCoO 2 cathode, and the Conformal Decomposition Finite Element Method is used to automatically generate computational meshes on this reconstructed microstructure. Replacement of the ideal solution Fickian diffusion model, typically used in battery simulations, with a more general non-ideal solution model shows substantially smaller gradients of lithium within particles than is typically observed in the literature. Using this more general model, lithium gradients only appear at states of charge where the open-circuit voltage is relatively constant. While lithium gradients do affect the mechanical stress state in the particles, the maximum stresses are always found in the fully-charged state and are strongly affected by the local details of the microstructure and particle-to-particle contacts. These coupled electrochemical-mechanical simulations begin to yield insight into the partitioning of volume change between reducing pore space and macroscopically swelling the electrode. Lastly, preliminary studies that include the presence of the polymeric binder suggest that it can greatly impact stress generation and that it is an important area for future research.« less

The effect of impeller type on silica sol formation in laboratory scale agitated tank

NASA Astrophysics Data System (ADS)

Nurtono, Tantular; Suprana, Yayang Ade; Latif, Abdul; Dewa, Restu Mulya; Machmudah, Siti; Widiyastuti, Winardi, Sugeng

2016-02-01

The multiphase polymerization reaction of the silica sol formation produced from silicic acid and potassium hydroxide solutions in laboratory scale agitated tank was studied. The reactor is equipped with four segmental baffle and top entering impeller. The inside diameter of reactor is 9 cm, the baffle width is 0.9 cm, and the impeller position is 3 cm from tank bottom. The diameter of standard six blades Rushton and three blades marine propeller impellers are 5 cm. The silicic acid solution was made from 0.2 volume fraction of water glass (sodium silicate) solution in which the sodium ion was exchanged by hydrogen ion from cation resin. The reactor initially filled with 286 ml silicic acid solution was operated in semi batch mode and the temperature was kept constant in 60 °C. The 3 ml/minute of 1 M potassium hydroxide solution was added into stirred tank and the solution was stirred. The impeller rotational speed was varied from 100 until 700 rpm. This titration was stopped if the solution in stirred tank had reached the pH of 10-The morphology of the silica particles in the silica sol product was analyzed by Scanning Electron Microscope (SEM). The size of silica particles in silica sol was measured based on the SEM image. The silica particle obtained in this research was amorphous particle and the shape was roughly cylinder. The flow field generated by different impeller gave significant effect on particle size and shape. The smallest geometric mean of length and diameter of particle (4.92 µm and 2.42 µm, respectively) was generated in reactor with marine propeller at 600 rpm. The reactor with Rushton impeller produced particle which the geometric mean of length and diameter of particle was 4.85 µm and 2.36 µm, respectively, at 150 rpm.

The effect of impeller type on silica sol formation in laboratory scale agitated tank

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nurtono, Tantular; Suprana, Yayang Ade; Latif, Abdul

2016-02-08

The multiphase polymerization reaction of the silica sol formation produced from silicic acid and potassium hydroxide solutions in laboratory scale agitated tank was studied. The reactor is equipped with four segmental baffle and top entering impeller. The inside diameter of reactor is 9 cm, the baffle width is 0.9 cm, and the impeller position is 3 cm from tank bottom. The diameter of standard six blades Rushton and three blades marine propeller impellers are 5 cm. The silicic acid solution was made from 0.2 volume fraction of water glass (sodium silicate) solution in which the sodium ion was exchanged by hydrogen ion from cationmore » resin. The reactor initially filled with 286 ml silicic acid solution was operated in semi batch mode and the temperature was kept constant in 60 °C. The 3 ml/minute of 1 M potassium hydroxide solution was added into stirred tank and the solution was stirred. The impeller rotational speed was varied from 100 until 700 rpm. This titration was stopped if the solution in stirred tank had reached the pH of 10-The morphology of the silica particles in the silica sol product was analyzed by Scanning Electron Microscope (SEM). The size of silica particles in silica sol was measured based on the SEM image. The silica particle obtained in this research was amorphous particle and the shape was roughly cylinder. The flow field generated by different impeller gave significant effect on particle size and shape. The smallest geometric mean of length and diameter of particle (4.92 µm and 2.42 µm, respectively) was generated in reactor with marine propeller at 600 rpm. The reactor with Rushton impeller produced particle which the geometric mean of length and diameter of particle was 4.85 µm and 2.36 µm, respectively, at 150 rpm.« less

Luminescence from edge fracture in shocked lithium fluoride crystals

DOE PAGES

Turley, W. D.; Stevens, G. D.; Capelle, G. A.; ...

2013-04-03

Light emitted from a [100] lithium fluoride crystal was characterized under shock wave compression to 28 GPa followed by complete stress release at the edges. We examined the light using time-gated optical spectrometry and imaging, time-resolved optical emission measurements, and hydrodynamic modeling. The shock arrival at the circumference of the crystal was delayed relative to the center so that the two regions could be studied at different times. The majority of the light emission originated when the shock waves released at the circumference of the crystal. Unlike previously reported results for shocked lithium fluoride, we found that the light spectrummore » is not strictly broad band, but has spectral lines associated with atomic lithium in addition to a broad band background. Also, the emission spectrum depends strongly on the gas surrounding the sample. Based on our observations, the line emission appears to be related to fracture of the lithium fluoride crystal from the shock wave releasing at the edges. Moreover, experimenters frequently utilize lithium fluoride crystals as transparent windows for observing shock compressed samples. Because of the experimental geometries used, the shock wave in such cases often reaches the circumference of the window at nearly the same moment as when it reaches the center of the sample-window interface. Light generated at the circumference could contaminate the measurement at the interface when this light scatters into the observed region. Finally, this background light may be reduced or avoided using experimental geometries which delay the arrival of the shock wave at the edges of the crystal.« less

Months between rejuvenation and volcanic eruption at Yellowstone caldera, Wyoming

USGS Publications Warehouse

Till, Christy B.; Vazquez, Jorge A.; Boyce, Jeremy W

2015-01-01

Rejuvenation of previously intruded silicic magma is an important process leading to effusive rhyolite, which is the most common product of volcanism at calderas with protracted histories of eruption and unrest such as Yellowstone, Long Valley, and Valles, USA. Although orders of magnitude smaller in volume than rare caldera-forming super-eruptions, these relatively frequent effusions of rhyolite are comparable to the largest eruptions of the 20th century and pose a considerable volcanic hazard. However, the physical pathway from rejuvenation to eruption of silicic magma is unclear particularly because the time between reheating of a subvolcanic intrusion and eruption is poorly quantified. This study uses geospeedometry of trace element profiles with nanometer resolution in sanidine crystals to reveal that Yellowstone’s most recent volcanic cycle began when remobilization of a near- or sub-solidus silicic magma occurred less than 10 months prior to eruption, following a 220,000 year period of volcanic repose. Our results reveal a geologically rapid timescale for rejuvenation and effusion of ~3 km3 of high-silica rhyolite lava even after protracted cooling of the subvolcanic system, which is consistent with recent physical modeling that predict a timescale of several years or less. Future renewal of rhyolitic volcanism at Yellowstone is likely to require an energetic intrusion of mafic or silicic magma into the shallow subvolcanic reservoir and could rapidly generate an eruptible rhyolite on timescales similar to those documented here.

Synthesis of Non-Toxic Silica Particles Stabilized by Molecular Complex Oleic-Acid/Sodium Oleate

PubMed Central

Spataru, Catalin Ilie; Ianchis, Raluca; Petcu, Cristian; Nistor, Cristina Lavinia; Purcar, Violeta; Trica, Bogdan; Nitu, Sabina Georgiana; Somoghi, Raluca; Alexandrescu, Elvira; Oancea, Florin; Donescu, Dan

2016-01-01

The present work is focused on the preparation of biocompatible silica particles from sodium silicate, stabilized by a vesicular system containing oleic acid (OLA) and its alkaline salt (OLANa). Silica nanoparticles were generated by the partial neutralization of oleic acid (OLA), with the sodium cation present in the aqueous solutions of sodium silicate. At the molar ratio OLA/Na+ = 2:1, the molar ratio (OLA/OLANa = 1:1) required to form vesicles, in which the carboxyl and carboxylate groups have equal concentrations, was achieved. In order to obtain hydrophobically modified silica particles, octadecyltriethoxysilane (ODTES) was added in a sodium silicate sol–gel mixture at different molar ratios. The interactions between the octadecyl groups from the modified silica and the oleyl chains from the OLA/OLANa stabilizing system were investigated via simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC) (TG-DSC) analyses.A significant decrease in vaporization enthalpy and an increase in amount of ODTES were observed. Additionally, that the hydrophobic interaction between OLA and ODTES has a strong impact on the hybrids’ final morphology and on their textural characteristics was revealed. The highest hydrodynamic average diameter and the most negative ζ potential were recorded for the hybrid in which the ODTES/sodium silicate molar ratio was 1:5. The obtained mesoporous silica particles, stabilized by the OLA/OLANa vesicular system, may find application as carriers for hydrophobic bioactive molecules. PMID:27869768

Nanoprocess and nanoscale surface functionalization on cathode materials for advanced lithium-ion batteries.

PubMed

Alaboina, Pankaj Kumar; Uddin, Md-Jamal; Cho, Sung-Jin

2017-10-26

Nanotechnology-driven development of cathode materials is an essential part to revolutionize the evolution of the next generation lithium ion batteries. With the progress of nanoprocess and nanoscale surface modification investigations on cathode materials in recent years, the advanced battery technology future seems very promising - Thanks to nanotechnology. In this review, an overview of promising nanoscale surface deposition methods and their significance in surface functionalization on cathodes is extensively summarized. Surface modified cathodes are provided with a protective layer to overcome the electrochemical performance limitations related to side reactions with electrolytes, reduce self-discharge reactions, improve thermal and structural stability, and further enhance the overall battery performance. The review addresses the importance of nanoscale surface modification on battery cathodes and concludes with a comparison of the different nanoprocess techniques discussed to provide a direction in the race to build advanced lithium-ion batteries.

Molten Salt Electrolytically Produced Carbon/Tin Nanomaterial as the Anode in a Lithium Ion Battery

NASA Astrophysics Data System (ADS)

Das Gupta, Rajshekar; Schwandt, Carsten; Fray, Derek J.

2017-03-01

A carbon/tin nanomaterial, consisting of predominantly Sn-filled carbon nanotubes and nanoparticles, is prepared by molten salt electrochemistry, using electrodes of graphite and an electrolyte of LiCl salt containing a small admixture of SnCl2. The C/Sn hybrid material generated is incorporated into the active anode material of a lithium ion battery and tested with regard to storage capacity and cycling behavior. The results demonstrate that the C/Sn material has favorable properties, in terms of energy density and in particular long-term stability, that exceed those of the individual components alone. The initial irreversible capacity of the material is somewhat larger than that of conventional battery graphite which is due to its unique nanostructure. Overall the results would indicate the suitability of this material for use in the anodes of lithium ion batteries with high rate capability.

Si/Ge double-layered nanotube array as a lithium ion battery anode.

PubMed

Song, Taeseup; Cheng, Huanyu; Choi, Heechae; Lee, Jin-Hyon; Han, Hyungkyu; Lee, Dong Hyun; Yoo, Dong Su; Kwon, Moon-Seok; Choi, Jae-Man; Doo, Seok Gwang; Chang, Hyuk; Xiao, Jianliang; Huang, Yonggang; Park, Won Il; Chung, Yong-Chae; Kim, Hansu; Rogers, John A; Paik, Ungyu

2012-01-24

Problems related to tremendous volume changes associated with cycling and the low electron conductivity and ion diffusivity of Si represent major obstacles to its use in high-capacity anodes for lithium ion batteries. We have developed a group IVA based nanotube heterostructure array, consisting of a high-capacity Si inner layer and a highly conductive Ge outer layer, to yield both favorable mechanics and kinetics in battery applications. This type of Si/Ge double-layered nanotube array electrode exhibits improved electrochemical performances over the analogous homogeneous Si system, including stable capacity retention (85% after 50 cycles) and doubled capacity at a 3C rate. These results stem from reduced maximum hoop strain in the nanotubes, supported by theoretical mechanics modeling, and lowered activation energy barrier for Li diffusion. This electrode technology creates opportunities in the development of group IVA nanotube heterostructures for next generation lithium ion batteries. © 2011 American Chemical Society

High Voltage Li-Ion Battery Using Exfoliated Graphite/Graphene Nanosheets Anode.

PubMed

Agostini, Marco; Brutti, Sergio; Hassoun, Jusef

2016-05-04

The achievement of a new generation of lithium-ion battery, suitable for a continuously growing consumer electronic and sustainable electric vehicle markets, requires the development of new, low-cost, and highly performing materials. Herein, we propose a new and efficient lithium-ion battery obtained by coupling exfoliated graphite/graphene nanosheets (EGNs) anode and high-voltage, spinel-structure cathode. The anode shows a capacity exceeding by 40% that ascribed to commercial graphite in lithium half-cell, at very high C-rate, due to its particular structure and morphology as demonstrated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The Li-ion battery reveals excellent efficiency and cycle life, extending up to 150 cycles, as well as an estimated practical energy density of about 260 Wh kg(-1), that is, a value well exceeding the one associated with the present-state Li-ion battery.

Artificial Solid Electrolyte Interphase-Protected LixSi Nanoparticles: An Efficient and Stable Prelithiation Reagent for Lithium-Ion Batteries.

PubMed

Zhao, Jie; Lu, Zhenda; Wang, Haotian; Liu, Wei; Lee, Hyun-Wook; Yan, Kai; Zhuo, Denys; Lin, Dingchang; Liu, Nian; Cui, Yi

2015-07-08

Prelithiation is an important strategy to compensate for lithium loss in lithium-ion batteries, particularly during the formation of the solid electrolyte interphase (SEI) from reduced electrolytes in the first charging cycle. We recently demonstrated that LixSi nanoparticles (NPs) synthesized by thermal alloying can serve as a high-capacity prelithiation reagent, although their chemical stability in the battery processing environment remained to be improved. Here we successfully developed a surface modification method to enhance the stability of LixSi NPs by exploiting the reduction of 1-fluorodecane on the LixSi surface to form a continuous and dense coating through a reaction process similar to SEI formation. The coating, consisting of LiF and lithium alkyl carbonate with long hydrophobic carbon chains, serves as an effective passivation layer in the ambient environment. Remarkably, artificial-SEI-protected LixSi NPs show a high prelithiation capacity of 2100 mA h g(-1) with negligible capacity decay in dry air after 5 days and maintain a high capacity of 1600 mA h g(-1) in humid air (∼10% relative humidity). Silicon, tin, and graphite were successfully prelithiated with these NPs to eliminate the irreversible first-cycle capacity loss. The use of prelithiation reagents offers a new approach to realize next-generation high-energy-density lithium-ion batteries.

Mechanical Deformation of a Lithium-Metal Anode Due to a Very Stiff Separator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferrese, A; Newman, J

2014-05-21

This work builds on the two-dimensional model presented by Ferrese et al. [J. Electrochem. Soc., 159, A1615 (2012)1, which captures the movement of lithium metal at the negative electrode during cycling in a Li-metal/LiCoO2 cell. In this paper, the separator is modeled as a dendrite-inhibiting polymer separator with an elastic modulus of 16 GPa. The separator resists the movement of lithium through the generation of stresses in the cell. These stresses affect the negative electrode through two mechanisms altering the thermodynamics of the negative electrode and deforming the negative electrode mechanically. From this analysis, we find that the dendrite-inhibiting separatormore » causes plastic and elastic deformation of the lithium at the negative electrode which flattens the electrode considerably when compared to the liquid-electrolyte case. This flattening of the negative electrode causes only very slight differences in the local state of charge in the positive electrode. When comparing the magnitude of the effects flattening the negative electrode, we find that the plastic deformation plays a much larger role than either the pressure-modified reaction kinetics or elastic deformation. This is due to the low yield strength of the lithium metal, which limits the stresses such that they have only a small effect on the reaction kinetics. (C) 2014 The Electrochemical Society. All rights reserved.« less

Cleaning techniques for intense ion beam sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Menge, P.R.; Cuneo, M.E.; Bailey, J.E.

Generation of high power lithium ion beams on the SABRE (1TW) and PBFA-X (20 TW) accelerators have been limited by the parallel acceleration of contaminant ions. during the beam pulse lithium is replaced by protons and carbon ions. This replacement is accompanied by rapid impedance decay of the diode. The contaminant hydrogen and carbon is believed to originate from impurity molecules on the surface and in the bulk of the lithium ion source and its substrate material. Cleaning techniques designed to remove hydrocarbons from the ion source have been employed with some success in test stand experiments and on SABRE.more » The test stand experiments have shown that a lithium fluoride (LiF) ion source film can accrue dozens of hydrocarbon monolayers on its surface while sitting in vacuum. Application of 13.5 MHz RF discharge cleaning with 90% Ar/10% O{sub 2} can significantly reduce the surface hydrocarbon layers on the LiF film. On SABRE, combinations of RF discharge cleaning, anode heating, layering gold between the source film (LiF) and its substrate, and cryogenic cathode cooling produced an increase by a factor of 1.5--2 in the quantity of high energy lithium in the ion beam. A corresponding decrease in protons and carbon ions was also observed. Cleaning experiments on PBFA-X are underway. New designs of contamination resistant films and Li ion sources are currently being investigated.« less

Selective recovery of cobalt, nickel and lithium from sulfate leachate of cathode scrap of Li-ion batteries using liquid-liquid extraction

NASA Astrophysics Data System (ADS)

Nguyen, Viet Tu; Lee, Jae-chun; Jeong, Jinki; Kim, Byung-Su; Pandey, B. D.

2014-03-01

This paper focuses on the extractive separation and selective recovery of cobalt, nickel and lithium from the sulfate leachate of cathode scrap generated during manufacture of lithium ion batteries (LIBs). The conditions for extraction, scrubbing and stripping of cobalt from nickel and lithium are optimized with an aqueous feed containing 25.1 g·dm-3 cobalt, 2.54 g·dm-3 nickel and 6.2 g·dm-3 lithium using Na-PC-88A. 99.8% Co is extracted with 60% Na-0.56 mol·dm-3 PC-88A in two counter-current stages at an O/A phase ratio of 3/1 and an equilibrium pH of 4.5. The "crowding effect" shown for the first time provides effective scrubbing of impurities (Ni and Li) with 2.0 g·dm-3 CoSO4 solution. The McCabe-Thiele diagram predicts the scrubbing of 99.9% Ni and 99.9% Li at an equilibrium pH of 4.75 and O/A of 2/1 in two stages. High purity (99.9%) cobalt sulfate along with Ni and Li from the leach liquor of cathode scrap is recovered by solvent extraction. The proposed process ensures complete recycling of the waste of the manufacturing process of LIBs.

[Lithium and anticonvulsants in bipolar depression].

PubMed

Samalin, L; Nourry, A; Llorca, P-M

2011-12-01

For decades, lithium and anticonvulsants have been widely used in the treatment of bipolar disorder. Their efficacy in the treatment of mania is recognized. These drugs have been initially evaluated in old and methodologically heterogeneous studies. Their efficacy in bipolar depression has not always been confirmed in more recent and methodologically more reliable studies. Thus, lithium's efficacy as monotherapy was challenged by the study of Young (2008) that showed a lack of efficacy compared with placebo in the treatment of bipolar depression. In two recent meta-analyses, valproate has shown a modest efficacy in the treatment of bipolar depression. As for lithium, valproate appeared to have a larger antimanic effect for acute phase and prophylaxis of bipolar disorder. In contrast, lamotrigine is more effective on the depressive pole of bipolar disorder with better evidence for the prevention of depressive recurrences. The guidelines include these recent studies and recommend lamotrigine as a first-line treatment of bipolar depression and for maintenance treatment. Because of more discordant data concerning lithium and valproate, these two drugs are placed either as first or as second line treatment of bipolar depression. The different safety/efficacy ratios of mood stabilizers underlie the complementarity and the importance of combination between them, or with some second-generation antipsychotics, in the treatment of patients with bipolar disorder. Copyright © 2011 L’Encéphale. Published by Elsevier Masson SAS.. All rights reserved.

Stereoregulations of pyrimidinone based chiral auxiliary in aldol and alkylation reactions: a convenient route to oxyneolignans.

PubMed

Chouhan, Mangilal; Sharma, Ratnesh; Nair, Vipin A

2012-11-16

(S)-4-Isopropyl-1-phenyltetrahydropyrimidin-2(1H)-one was synthesized and evaluated as a chiral auxiliary for asymmetric acetate and propionate aldol reactions, by generation of titanium and lithium enolates, affording excellent yields and stereoselectivities for syn and anti aldol diastereomers, respectively. High stereoselectivities were also obtained in lithium mediated alkylation reactions. The application of the auxiliary was exemplified in the asymmetric synthesis of a natural oxyneolignan, (+)-(7S,8S)-4-hydroxy-3,3',5'-trimethoxy-8',9'-dinor-8,4'-oxyneoligna-7,9-diol-7'-oic acid.

Coupling of Mechanical Behavior of Lithium Ion Cells to Electrochemical-Thermal (ECT) Models for Battery Crush

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Chao; Santhanagopalan, Shriram; Pesaran, Ahmad

Vehicle crashes can lead to crushing of the battery, damaging lithium ion battery cells and causing local shorts, heat generation, and thermal runaway. Simulating all the physics and geometries at the same time is challenging and takes a lot of effort; thus, simplifications are needed. We developed a material model for simultaneously modeling the mechanical-electrochemical-thermal behavior, which predicted the electrical short, voltage drop, and thermal runaway behaviors followed by a mechanical abuse-induced short. The effect of short resistance on the battery cell performance was studied.

Nanosatellite Power System Considerations

NASA Technical Reports Server (NTRS)

Robyn, M.; Thaller, L.; Scott, D.

1995-01-01

The capability to build complex electronic functions into compact packages is opening the path to miniature satellites on the order of 1 kg mass, 10 cm across, packed with the computing processors, motion controllers, measurement sensors, and communications hardware necessary for operation. Power generation will be from short strings of silicon or gallium arsenide-based solar photovoltaic cells with the array power maximized by a peak power tracker (PPT). Energy storage will utilize a low voltage battery with nickel cadmium or lithium ion cells as the most likely selections for rechargeables and lithium (MnO2-Li) primary batteries for one shot short missions.

Thermal behavior of an experimental 2.5-kWh lithium/iron sulfide battery

NASA Astrophysics Data System (ADS)

Chen, C. C.; Olszanski, T. W.; Gibbard, H. F.

1981-10-01

The thermal energy generation and the gross thermal energy balance in the battery systems was studied. High temperature lithium/iron sulfide batteries for electric vehicle applications were developed. The preferred battery temperature range during operation and idle periods is 400 to 500 C. Thermal management is an essential part of battery design, the battery requires a thermal insulation vessel to minimize heat loss and heating and cooling systems to control temperature. Results of temperature measurements performed on a 2.5-kWh battery module, which was built to gain information for the design of larger systems are reported.

Lithium niobate explosion monitor

DOEpatents

Bundy, Charles H.; Graham, Robert A.; Kuehn, Stephen F.; Precit, Richard R.; Rogers, Michael S.

1990-01-01

Monitoring explosive devices is accomplished with a substantially z-cut lithium niobate crystal in abutment with the explosive device. Upon impact by a shock wave from detonation of the explosive device, the crystal emits a current pulse prior to destruction of the crystal. The current pulse is detected by a current viewing transformer and recorded as a function of time in nanoseconds. In order to self-check the crystal, the crystal has a chromium film resistor deposited thereon which may be heated by a current pulse prior to detonation. This generates a charge which is detected by a charge amplifier.

Lithium niobate explosion monitor

DOEpatents

Bundy, C.H.; Graham, R.A.; Kuehn, S.F.; Precit, R.R.; Rogers, M.S.

1990-01-09

Monitoring explosive devices is accomplished with a substantially z-cut lithium niobate crystal in abutment with the explosive device. Upon impact by a shock wave from detonation of the explosive device, the crystal emits a current pulse prior to destruction of the crystal. The current pulse is detected by a current viewing transformer and recorded as a function of time in nanoseconds. In order to self-check the crystal, the crystal has a chromium film resistor deposited thereon which may be heated by a current pulse prior to detonation. This generates a charge which is detected by a charge amplifier. 8 figs.

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Picosecond laser with active mode locking and calcium lithium niobium gallium disordered Nd3+-activated garnet

NASA Astrophysics Data System (ADS)

Basiev, Tasoltan T.; Grudinin, A. B.; Karasik, Aleksandr Ya; Senatorov, A. K.; Sobol, A. A.; Fedorov, V. V.; Shubochkin, R. L.

1994-01-01

A laser was constructed in which the active medium was a crystal of calcium lithium niobium gallium garnet activated with Nd3+ ions. An acoustooptic modulator made of an LiNbO3 crystal and a passive LiF switch with F2 colour centres were used in this laser. The combination of active mode locking and Q switching made it possible to generate laser pulses of 10-15 ps duration at the wavelength λ = 1061.2 nm with a peak power of about 15 MW.

Nanohybrids of magnetic iron-oxide particles in hydrophobic organoclays for oil recovery.

PubMed

Hsu, Ru-Siou; Chang, Wen-Hsin; Lin, Jiang-Jen

2010-05-01

Nanohybrids with magnetic iron-oxide nanoparticles (FeNPs) embedded in the multilayered silicate clay were synthesized by in situ Fe(2+)/Fe(3+) coprecipitation. The natural clay, sodium montmorillonite (Na(+)-MMT), was first modified with hydrophobic poly(oxypropylene)amine salts (POP at 2000 and 4000 g/mol M(w)). The two POP-intercalated organoclays, with a silicate interlayer expansion from 1.2 to 5.2 and 9.2 nm, respectively, are suitable for embedding FeNPs. The presence of POP organics in layered structure created the space for intercalating with FeNPs of 2-4 nm in diameter, observed by transmission electronic microscope. The synthesized nanohybrids of POP4000/MMT-FeNP was composed of 17% iron oxide and 51 wt % POP within the silicate basal spacing of 5.0 nm. In contrast, the lower molecular weight of POP2000 intercalated MMT failed to encapsulate FeNPs in a significant amount, but resulting a "crowding-out effect" that caused the silicate interlayer space to shrink from 5.2 to 1.8 nm because of the replacement of the POP salt by Fe(2+)/Fe(3+) ions. The synthesis required the use of high molecular weight POP4000 and low temperatures (<4 degrees C) for a better dispersion in the reaction medium. The presence of POP in the layered silicate facilitated a homogeneous POP/MMT in water, associating with Fe(2+)/Fe(3+) ions and spatially accommodating for the subsequently generated FeNPs. The synthesized nanostructure consisting of POP and FeNP could be used as a pollutant remedy because of its ability to adsorbing crude oil and it is maneuverable under an applied magnetism.

Extremely frequency-widened terahertz wave generation using Cherenkov-type radiation.

PubMed

Suizu, Koji; Koketsu, Kaoru; Shibuya, Takayuki; Tsutsui, Toshihiro; Akiba, Takuya; Kawase, Kodo

2009-04-13

Terahertz (THz) wave generation based on nonlinear frequency conversion is promising way for realizing a tunable monochromatic bright THz-wave source. Such a development of efficient and wide tunable THz-wave source depends on discovery of novel brilliant nonlinear crystal. Important factors of a nonlinear crystal for THz-wave generation are, 1. High nonlinearity and 2. Good transparency at THz frequency region. Unfortunately, many nonlinear crystals have strong absorption at THz frequency region. The fact limits efficient and wide tunable THz-wave generation. Here, we show that Cherenkov radiation with waveguide structure is an effective strategy for achieving efficient and extremely wide tunable THz-wave source. We fabricated MgO-doped lithium niobate slab waveguide with 3.8 microm of thickness and demonstrated difference frequency generation of THz-wave generation with Cherenkov phase matching. Extremely frequency-widened THz-wave generation, from 0.1 to 7.2 THz, without no structural dips successfully obtained. The tuning frequency range of waveguided Cherenkov radiation source was extremely widened compare to that of injection seeded-Terahertz Parametric Generator. The tuning range obtained in this work for THz-wave generation using lithium niobate crystal was the widest value in our knowledge. The highest THz-wave energy obtained was about 3.2 pJ, and the energy conversion efficiency was about 10(-5) %. The method can be easily applied for many conventional nonlinear crystals, results in realizing simple, reasonable, compact, high efficient and ultra broad band THz-wave sources.

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.; ...

2017-05-12

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Formation of wadsleyite in a shock experiment - implications for the duration of shock events in meteorite parent bodies

NASA Astrophysics Data System (ADS)

Tschauner, O.; Asimow, P. D.; Ahrens, T. J.; Kostandova, N.; Sinogeikin, S.

2007-12-01

We report the first observation of the high-pressure silicate phase wadsleyite in the recovery products of a shock experiment. Wadsleyite was detected by micro-X ray diffraction and EBSD. Wadsleyite grew from melt which formed by chemical reaction of periclase and silica during shock. Our findings show that the growth rate of high pressure silicate phases in shock-generated melts can be of the order of m/s and is probably not diffusion controlled. Our finding has important implications for the time scale of shock events recorded by meteorites and indicates that the presence of high pressure silicates found in shocked meteorites does not necessarily imply large impactor sizes. This work was supported by the NNSA Cooperative Agreement DOE-FC88-01NV14049 and NASA/Goddard grants under awards NNG04GP57G and NNG04GI07G. Use of the HPCAT facility was supported by DOE-BES, DOE-NNSA, NSF, DOD -TACOM, and the W.M. Keck Foundation. APS is supported by DOE-BES under Contract No. W-31-109-Eng-38.

Evidence for seismogenic fracture of silicic magma.

PubMed

Tuffen, Hugh; Smith, Rosanna; Sammonds, Peter R

2008-05-22

It has long been assumed that seismogenic faulting is confined to cool, brittle rocks, with a temperature upper limit of approximately 600 degrees C (ref. 1). This thinking underpins our understanding of volcanic earthquakes, which are assumed to occur in cold rocks surrounding moving magma. However, the recent discovery of abundant brittle-ductile fault textures in silicic lavas has led to the counter-intuitive hypothesis that seismic events may be triggered by fracture and faulting within the erupting magma itself. This hypothesis is supported by recent observations of growing lava domes, where microearthquake swarms have coincided with the emplacement of gouge-covered lava spines, leading to models of seismogenic stick-slip along shallow shear zones in the magma. But can fracturing or faulting in high-temperature, eruptible magma really generate measurable seismic events? Here we deform high-temperature silica-rich magmas under simulated volcanic conditions in order to test the hypothesis that high-temperature magma fracture is seismogenic. The acoustic emissions recorded during experiments show that seismogenic rupture may occur in both crystal-rich and crystal-free silicic magmas at eruptive temperatures, extending the range of known conditions for seismogenic faulting.

Dust Destruction in the ISM: A Re-Evaluation of Dust Lifetimes

NASA Technical Reports Server (NTRS)

Jones, A. P.; Nuth, J. A., III

2011-01-01

There is a long-standing conundrum in interstellar dust studies relating to the discrepancy between the time-scales for dust formation from evolved stars and the apparently more rapid destruction in supernova-generated shock waves. Aims. We re-examine some of the key issues relating to dust evolution and processing in the interstellar medium. Methods. We use recent and new constraints from observations, experiments, modelling and theory to re-evaluate dust formation in the interstellar medium (ISM). Results. We find that the discrepancy between the dust formation and destruction time-scales may not be as significant as has previously been assumed because of the very large uncertainties involved. Conclusions. The derived silicate dust lifetime could be compatible with its injection time-scale, given the inherent uncertainties in the dust lifetime calculation. The apparent need to re-form significant quantities of silicate dust in the tenuous interstellar medium may therefore not be a strong requirement. Carbonaceous matter, on the other hand, appears to be rapidly recycled in the ISM and, in contrast to silicates, there are viable mechanisms for its re-formation in the ISM.

Geographic variation in the relationships of temperature, salinity or sigma sub t versus plant nutrient concentrations in the world ocean. [silicic acid, nitrate, and phosphate concentration

NASA Technical Reports Server (NTRS)

Kamykowski, D.; Zentara, S. J.

1985-01-01

A NODC data set representing all regions of the world ocean was analyzed for temperature and sigma-t relationships with nitrate, phosphate or silicic acid. Six cubic regressions were for each ten degree square of latitude and longitude containing adequate data. World maps display the locations that allow the prediction of plant nutrient concentrations from temperature or sigma-t. Geographic coverage improves along the sequence: nitrate, phosphate, and silicic acid and is better for sigma-t than for temperature. Contour maps of the approximate temperature of sigma-t at which these nitrients are no longer measurable in a parcel of water are generated, based on a percentile analysis of the temperature or sigma-t at which less than a selected amount of plant nutrient occurs. Results are stored on magnetic tape in tabular form. The global potential to predict plant nutrient concentrations from remotely sensed temperature of sigma-t and to emphasize the latitudinally and longitudinally changing phytoplankton growth environment in present and past oceans is demonstrated.

Molar volume, excess enthalpy, and Prigogine-Defay ratio of some silicate glasses with different (P,T) histories.

PubMed

Wondraczek, Lothar; Behrens, Harald

2007-10-21

Structural relaxation in silicate glasses with different (p,T) histories was experimentally examined by differential scanning calorimetry and measurements of molar volume under ambient pressure. Temperature and pressure-dependent rates of changes in molar volume and generation of excess enthalpy were determined for sodium trisilicate, soda lime silicate, and sodium borosilicate (NBS) compositions. From the derived data, Prigogine-Defay ratios are calculated and discussed. Changes of excess enthalpy are governed mainly by changes in short-range structure, as is shown for NBS where boron coordination is highly sensitive to pressure. For all three glasses, it is shown how the relaxation functions that underlie volume, enthalpy, and structural relaxation decouple for changes in cooling rates and pressure of freezing, respectively. The magnitude of the divergence between enthalpy and volume may be related to differences in structural sensitivity to changes in the (p,V,T,t) space on different length scales. The findings suggest that the Prigogine-Defay ratio is related to the magnitude of the discussed decoupling effect.

Generating High-Brightness Ion Beams for Inertial Confinement Fusion

NASA Astrophysics Data System (ADS)

Cuneo, M. E.

1997-11-01

The generation of high current density ion beams with applied-B ion diodes showed promise in the late-1980's as an efficient, rep-rate, focusable driver for inertial confinement fusion. These devices use several Tesla insulating magnetic fields to restrict electron motion across anode-cathode gaps of order 1-2 cm, while accelerating ions to generate ≈ 1 kA/cm^2, 5 - 15 MeV beams. These beams have been used to heat hohlraums to about 65 eV. However, meeting the ICF driver requirements for low-divergence and high-brightness lithium ion beams has been more technically challenging than initially thought. Experimental and theoretical work over the last 5 years shows that high-brightness beams meeting the requirements for inertial confinement fusion are possible. The production of these beams requires the simultaneous integration of at least four conditions: 1) rigorous vacuum cleaning techniques for control of undesired anode, cathode, ion source and limiter plasma formation from electrode contaminants to control impurity ions and impedance collapse; 2) carefully tailored insulating magnetic field geometry for uniform beam generation; 3) high magnetic fields (V_crit/V > 2) and other techniques to control the electron sheath and the onset of a high divergence electromagnetic instability that couples strongly to the ion beam; and 4) an active, pre-formed, uniform lithium plasma for low source divergence which is compatible with the above electron-sheath control techniques. These four conditions have never been simultaneously present in any lithium beam experiment, but simulations and experimental tests of individual conditions have been done. The integration of these conditions is a goal of the present ion beam generation program at Sandia. This talk will focus on the vacuum cleaning techniques for ion diodes and pulsed power devices in general, including experimental results obtained on the SABRE and PBFA-II accelerators over the last 3 years. The current status of integration of the other key physics and technologies required to demonstrate high-brightness ion beams will also be presented.

Sensitive Infrared Signal Detection by Upconversion Technique

NASA Technical Reports Server (NTRS)

Wong, Teh-Hwa; Yu, Jirong; Bai, Yingxin; Johnson, William; Chen, Songsheng; Petros, Mulugeta; Singh, Upendra N.

2014-01-01

We demonstrated upconversion assisted detection of a 2.05-micron signal by sum frequency generation to generate a 700-nm light using a bulk periodically poled lithium niobate crystal. The achieved 94% intrinsic upconversion efficiency and 22.58% overall detection efficiency at a pW level of 2.05 micron pave the path to detect extremely weak infrared (IR) signals for remote sensing applications.

Next Generation Anodes for Lithium Ion Batteries: Thermodynamic Understanding and Abuse Performance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fenton, Kyle R.; Allcorn, Eric; Nagasubramanian, Ganesan

The objectives of this project are to elucidate degradation mechanisms, decomposition products, and abuse response for next generation silicon based anodes; and understand the contribution of various materials properties and cell build parameters towards thermal runaway enthalpies. Quantify the contributions from various cell parameters such as particle size, composition, state of charge (SOC), electrolyte to active materials ratio, etc.

Evaluation of a solar intermittent refrigeration system for ice production operating with ammonia/lithium nitrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rivera, W.; Moreno-Quintanar, G.; Best, R.

2011-01-15

A novel solar intermittent refrigeration system for ice production developed in the Centro de Investigacion en Energia of the Universidad Nacional Autonoma de Mexico is presented. The system operates with the ammonia/lithium nitrate mixture. The system developed has a nominal capacity of 8 kg of ice/day. It consists of a cylindrical parabolic collector acting as generator-absorber. Evaporator temperatures as low as -11 C were obtained for several hours with solar coefficients of performance up to 0.08. It was found that the coefficient of performance increases with the increment of solar radiation and the solution concentration. A dependency of the coefficientmore » of performance was not founded against the cooling water temperature. Also it was found that the maximum operating pressure increases meanwhile the generation temperature decreases with an increase of the solution concentration. (author)« less

Polarization entangled cluster state generation in a lithium niobate chip

NASA Astrophysics Data System (ADS)

Szep, Attila; Kim, Richard; Shin, Eunsung; Fanto, Michael L.; Osman, Joseph; Alsing, Paul M.

2016-10-01

We present a design of a quantum information processing C-phase (Controlled-phase) gate applicable for generating cluster states that has a form of integrated photonic circuits assembled with cascaded directional couplers on a Ti in-diffused Lithium Niobate (Ti-LN) platform where directional couplers as the integrated optical analogue of bulk beam splitters are used as fundamental building blocks. Based on experimentally optimized fabrication parameters of Ti-LN optical waveguides operating at an 810nm wavelength, an integrated Ti-LN quantum C-phase gate is designed and simulated. Our proposed C-phase gate consists of three tunable directional couplers cascaded together with having different weighted switching ratios for providing a tool of routing vertically- and horizontally-polarized photons independently. Its operation mechanism relies on selectively controlling the optical coupling of orthogonally polarized modes via the change in the index of refraction, and its operation is confirmed by the BPM simulation.

Chemical dealloying synthesis of porous silicon anchored by in situ generated graphene sheets as anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Feng, Jinkui; Zhang, Zhen; Ci, Lijie; Zhai, Wei; Ai, Qing; Xiong, Shenglin

2015-08-01

A novel one-pot chemical dealloying method has been developed to prepare nanocomposite of reduced graphene oxide (RGO) and silicon dendrite from cheap commercial Al-Si eutectic precursor. The RGO anchoring could act as both conductive agent and buffer layer for Si volume change in the application of lithium ion batteries (LIBs). The Si/RGO composites show an initial reversible capacity of 2280 mAh g-1, excellent capacity retention of 1942 mAh g-1 even after 100 cycles, and a high capacity of 1521 mAh g-1 even at the rate of 4000 mA g-1. Electrochemical impedance spectroscopy (EIS) measurement proved that Si/RGO composite has the lower charge transfer resistance. This work proposes an economic and facile method to prepare silicon based anode material for next generation LIBs with high energy density.

Development of a solar powered residential air conditioner (General optimization)

NASA Technical Reports Server (NTRS)

Lowen, D. J.

1976-01-01

A commercially available 3-ton residential Lithium Bromide (LiBr) absorption air conditioner was modified for use with lower temperature solar heated water. The modification included removal of components such as the generator, concentration control chamber, liquid trap, and separator; and the addition of a Chrysler designed generator, an off-the-shelf LiBr-solution pump. The design goal of the modified unit was to operate with water as the heat-transfer fluid at a target temperature of 85 C (185 F), 29.4 C (85 F) cooling water inlet, producing 10.5 kW (3 tons) of cooling. Tests were performed on the system before and after modification to provide comparative data. At elevated temperatures (96 C, 205 F), the test results show that Lithium Bromide was carried into the condenser due to the extremely violent boiling and degraded the evaporator performance.

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Tianyuan; Xu, Gui-Liang; Li, Yan

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated frommore » the electrochemical oxidation are energetically unstable, and readily undergo a deprotonation reaction that generates protons and promote the dissolution of Al3+ from the aluminum foil. This new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.« less

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries

DOE PAGES

Ma, Tianyuan; Xu, Gui -Liang; Li, Yan; ...

2017-02-16

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated frommore » the electrochemical oxidation are energetically unstable, and readily undergo a deprotonation reaction that generates protons and promote the dissolution of Al 3+ from the aluminum foil. Finally, this new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.« less

Internal-short-mitigating current collector for lithium-ion battery

NASA Astrophysics Data System (ADS)

Wang, Meng; Le, Anh V.; Noelle, Daniel J.; Shi, Yang; Meng, Y. Shirley; Qiao, Yu

2017-05-01

Mechanical abuse often causes thermal runaway of lithium-ion battery (LIB). When a LIB cell is impacted, radial cracks can be formed in the current collector, separating the electrode into petals. As separator ruptures, the petals on positive and negative electrodes may contact each other, forming internal short circuit (ISC). In this study, we conducted an experimental investigation on LIB coin cells with current collectors modified by surface notches. Our testing results showed that as the current collector contained appropriate surface notches, the cracking mode of electrode in a damaged LIB cell could be adjusted. Particularly, if a complete circumferential crack was generated, the petals would be cut off, which drastically reduced the area of electrode involved in ISC and the associated heat generation rate. A parameterized study was performed to analysis various surface-notch configurations. We identified an efficient surface-notch design that consistently led to trivial temperature increase of ISC.

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries.

PubMed

Ma, Tianyuan; Xu, Gui-Liang; Li, Yan; Wang, Li; He, Xiangming; Zheng, Jianming; Liu, Jun; Engelhard, Mark H; Zapol, Peter; Curtiss, Larry A; Jorne, Jacob; Amine, Khalil; Chen, Zonghai

2017-03-02

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated from the electrochemical oxidation are energetically unstable and readily undergo a deprotonation reaction that generates protons and promotes the dissolution of Al 3+ from the aluminum foil. This new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.