Status of National Spherical Torus Experiment Liquid Lithium Divertor

NASA Astrophysics Data System (ADS)

Kugel, H. W.; Viola, M.; Ellis, R.; Bell, M.; Gerhardt, S.; Kaita, R.; Kallman, J.; Majeski, R.; Mansfield, D.; Roquemore, A. L.; Schneider, H.; Timberlake, J.; Zakharov, L.; Nygren, R. E.; Allain, J. P.; Maingi, R.; Soukhanovskii, V.

2009-11-01

Recent NSTX high power divertor experiments have shown significant and recurring benefits of solid lithium coatings on plasma facing components to the performance of divertor plasmas in both L- and H- mode confinement regimes heated by high-power neutral beams. The next step in this work is the 2009 installation of a Liquid Lithium Divertor (LLD). The 20 cm wide LLD located on the lower outer divertor, consists of four, 80 degree sections; each section is separated by a row of graphite diagnostic tiles. The temperature controlled LLD structure consists of a 0.01cm layer of vacuum flame-sprayed, 50 percent porous molybdenum, on top of 0.02 cm, 316-SS brazed to a 1.9 cm Cu base. The physics design of the LLD encompasses the desired plasma requirements, the experimental capabilities and conditions, power handling, radial location, pumping capability, operating temperature, lithium filling, MHD forces, and diagnostics for control and characterization.

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.

Lithium Circuit Test Section Design and Fabrication

NASA Technical Reports Server (NTRS)

Godfroy, Thomas; Garber, Anne

2006-01-01

The Early Flight Fission - Test Facilities (EFF-TF) team has designed and built an actively pumped lithium flow circuit. Modifications were made to a circuit originally designed for NaK to enable the use of lithium that included application specific instrumentation and hardware. Component scale freeze/thaw tests were conducted to both gain experience with handling and behavior of lithium in solid and liquid form and to supply anchor data for a Generalized Fluid System Simulation Program (GFSSP) model that was modified to include the physics for freeze/thaw transitions. Void formation was investigated. The basic circuit components include: reactor segment, lithium to gas heat exchanger, electromagnetic (EM) liquid metal pump, load/drain reservoir, expansion reservoir, instrumentation, and trace heaters. This paper will discuss the overall system design and build and the component testing findings.

Lithium Circuit Test Section Design and Fabrication

NASA Astrophysics Data System (ADS)

Godfroy, Thomas; Garber, Anne; Martin, James

2006-01-01

The Early Flight Fission - Test Facilities (EFF-TF) team has designed and built an actively pumped lithium flow circuit. Modifications were made to a circuit originally designed for NaK to enable the use of lithium that included application specific instrumentation and hardware. Component scale freeze/thaw tests were conducted to both gain experience with handling and behavior of lithium in solid and liquid form and to supply anchor data for a Generalized Fluid System Simulation Program (GFSSP) model that was modified to include the physics for freeze/thaw transitions. Void formation was investigated. The basic circuit components include: reactor segment, lithium to gas heat exchanger, electromagnetic (EM) liquid metal pump, load/drain reservoir, expansion reservoir, instrumentation, and trace heaters. This paper discusses the overall system design and build and the component testing findings.

Interaction of plasmas with lithium and tungsten fusion plasma facing components

NASA Astrophysics Data System (ADS)

Fiflis, Peter Robert

One of the largest outstanding issues in magnetic confinement fusion is the interaction of the fusion plasma with the first wall of the device; an interaction which is strongest in the divertor region. Erosion, melting, sputtering, and deformation are all concerns which inform choices of divertor material. Of the many materials proposed for use in the divertor, only a few remain as promising choices. Tungsten has been chosen as the material for the ITER divertor, and liquid lithium stands poised as its replacement in higher heat flux devices. As a refractory metal, tungsten's large melting point and thermal conductivity as well as its low sputtering yield have led to its selection as the material of choice of the ITER divertor. Experiments have reinforced this choice demonstrating tungsten's ability to withstand large heat fluxes when adequately cooled. However, tungsten has shown a propensity to nanostructure under exposure within a certain temperature range to large fluxes of helium ions. These nanostructures if disrupted into the plasma as dust by an off-normal event would cause quenching of the plasma from the generated dust. Liquid lithium, meanwhile, has gathered growing interest within the fusion community in recent years as a divertor, limiter, and alternative first wall material. Liquid lithium is attractive as a low-Z material replacement for refractory metals due to its ability to getter impurities, while also being self-healing in nature. However, concerns exist about the stability of a liquid metal surface at the edge of a fusion device. Liquid metal pools, such as the Li-DiMes probe, have shown evidence of macroscopic lithium displacement as well as droplet formation and ejection into the plasma. These issues must be mitigated in future implementations of liquid lithium divertor concepts. Rayleigh-Taylor-like (RT) and Kelvin-Helmholtz-like (KH) instabilities have been claimed as the initiators of droplet ejection, yet not enough data exists to delineate a stability boundary. The influences of plasma pressure and current driven instabilities on lithium surfaces that lead to droplet ejection are investigated to determine which of the two effects is dominant for a given set of plasma conditions. This work studies the influence of large plasma fluxes on these two materials to better inform the selection and design of plasma facing components (PFCs). The nanostructuring of tungsten was investigated to determine the mechanisms by which tungsten nanostructures so that its formation may be mitigated. Experiments investigated the dependence of nanostructuring on temperature, looked at the morphological evolution, and grew nanostructures on a variety of metals to examine their similarity to tungsten. Additionally, a computational model is presented for the initial stages of fuzz formation showing good quantitative and qualitative agreement with experimental observations. The influences of RT and KH instabilities on the surface of liquid lithium were experimentally observed and quantified on the ThermoElectric-driven Liquid-metal plasma-facing Structures (TELS) chamber at the University of Illinois at Urbana-Champaign and the stabilizing effect of surface tension, an effect employed by the LiMIT concept as well as other liquid lithium concepts, was studied, and the stability boundary afforded by surface tension was compared between experiment, computational simulation, and theory.

Study on High Speed Lithium Jet For Neutron Source of Boron Neutron Capture Therapy (BNCT)

NASA Astrophysics Data System (ADS)

Takahashi, Minoru; Kobayashi, Tooru; Zhang, Mingguang; Mák, Michael; Štefanica, Jirí; Dostál, Václav; Zhao, Wei

The feasibility study of a liquid lithium type proton beam target was performed for the neutron source of the boron neutron capture therapy (BNCT). As the candidates of the liquid lithium target, a thin sheet jet and a thin film flow on a concave wall were chosen, and a lithium flow experiment was conducted to investigate the hydrodynamic stability of the targets. The surfaces of the jets and film flows with a thickness of 0.5 mm and a width of 50 mm were observed by means of photography. It has been found that a stable sheet jet and a stable film flow on a concave wall can be formed up to certain velocities by using a straight nozzle and a curved nozzle with the concave wall, respectively.

Investigation of tin-lithium eutectic as a liquid plasma facing material

NASA Astrophysics Data System (ADS)

Ruzic, David; Szott, Matthew; Christenson, Michael; Shchelkanov, Ivan; Kalathiparambil, Kishor Kumar

2016-10-01

Innovative materials and techniques need to be utilized to address the high heat and particle flux incident on plasma facing components in fusion reactors. A liquid metal diverter module developed at UIUC with self circulating lithium has been successfully demonstrated to be capable of handling the relevant heat flux in plasma gun based tests and on operational tokamaks. The proper geometry of the liquid lithium trenches to minimize droplet ejection during transient plasma events have also been identified. Although lithium has proven to be effective in improved plasma performance and contributes to other advantageous factors like reduction in the fuel recycling, impurity gettering and, owing to the low Z, a significantly reduced impact on plasma as compared to the solid wall materials, it still poses several drawbacks related to its high reactivity and high vapor pressure at the relevant tokamak wall temperatures. The evaporation properties of a new eutectic mixture of tin and lithium (20% Sn) shows that lithium segregates to the surface at melting temperatures and hence is an effective replacement for pure lithium. Also, the vapor from the eutectic is dominated by lithium, minimizing the entry of high Z Sn into the plasma. At UIUC experiments for the synthesis and characterization of the eutectic - measurement of the critical wetting parameters and Seebeck coefficients with respect to the trench materials have been performed to ensure lithium wetting and flow in the trenches. The results will be presented. DOE project DEFG02- 99ER54515.

Conference Report on the 4rd International Symposium on Lithium Applications

NASA Astrophysics Data System (ADS)

Tabares, F. L.; Hirooka, Y.; Maingi, R.; Mazzitelli, G.; Mirnov, V.; Nygren, R.; Ono, M.; Ruzic, D. N.

2016-12-01

The fourth International Symposium on Liquid Metal Application for Fusion Devices (ISLA-2015) was held on 28-30 September 2015 at Granada, Spain, with growing participation and interest from the community working on general aspects of liquid metal research for fusion energy development. The ISLA symposia remain the largest, and arguably, the most important meetings dedicated to liquid metal application for the magnetic fusion research. Overall, 43 presentations plus 7 posters were given, representing 28 institutions from 12 countries. The latest experimental results from 9 magnetic fusion devices were given in 17 presentations from NSTX and LTX (PPPL, USA), FTU (ENEA, Italy), T-11M (Trinity, RF), T-10 (Kurchatov Institute, RF), TJ-II (CIEMAT, Spain), EAST (ASIPP, China), HT-7 (ASIPP, China), DIII-D (GA, USA), ISTTOK (IPFN, Portugal) and KTM (NNC RK, Kazakhstan). Sessions were devoted to the following: (I) liquid metals (LM) in magnetic confinement experiments (facility overviews), (II) LM in magnetic confinement experiments (topical issues), (III) laboratory experiments, (IV) LM tests in linear plasma devices, (V) LM theory/modeling (VI) LM technology and (VII) a special session on lithium-safety and lithium handling. There were contributions from fusion technology communities including IFMIF and TBM, which provided productive exchanges with physics-oriented magnetic confinement liquid metal research groups. This international workshop will continue on a biennial basis (alternating with the Plasma-Surface Interactions (PSI) Conference), with the next workshop scheduled for Moscow, Russian Federation, in 2017.

Plasma Surface Interactions Common to Advanced Fusion Wall Materials and EUV Lithography - Lithium and Tin

NASA Astrophysics Data System (ADS)

Ruzic, D. N.; Alman, D. A.; Jurczyk, B. E.; Stubbers, R.; Coventry, M. D.; Neumann, M. J.; Olczak, W.; Qiu, H.

2004-09-01

Advanced plasma facing components (PFCs) are needed to protect walls in future high power fusion devices. In the semiconductor industry, extreme ultraviolet (EUV) sources are needed for next generation lithography. Lithium and tin are candidate materials in both areas, with liquid Li and Sn plasma material interactions being critical. The Plasma Material Interaction Group at the University of Illinois is leveraging liquid metal experimental and computational facilities to benefit both fields. The Ion surface InterAction eXperiment (IIAX) has measured liquid Li and Sn sputtering, showing an enhancement in erosion with temperature for light ion bombardment. Surface Cleaning of Optics by Plasma Exposure (SCOPE) measures erosion and damage of EUV mirror samples, and tests cleaning recipes with a helicon plasma. The Flowing LIquid surface Retention Experiment (FLIRE) measures the He and H retention in flowing liquid metals, with retention coefficients varying between 0.001 at 500 eV to 0.01 at 4000 eV.

A thermo-electric-driven flowing liquid lithium limiter/divertor for magnetic confined fusion

NASA Astrophysics Data System (ADS)

Ruzic, D. N.; Xu, Wenyu; Curreli, Davide; Andruczyk, Daniel; Mui, Travis

2012-10-01

The concept of using a liquid metal, especially liquid lithium, as the plasma facing surface may provide the best path forward toward reactor designs. A liquid PFC can effectively eliminate the erosion and thermal stress problems compared to the solid PFC while transferring heat and prolong the lifetime limit of the PFCs. A liquid lithium surface can also suppress the hydrogen isotopes recycling and getter the impurities in fusion reactor. The Lithium/metal infused trench (LiMIT) concept successfully proved that the thermoelectric effect can induce electric currents inside liquid lithium and an external magnetic field can drive liquid lithium to flow within metallic open trenches. IR camera and thermocouple measurements prove the strong heat transfer ability of this concept. A new flowing lithium system with active control of the temperature gradient inside the lithium trenches and back flow channels has been designed. TEMHD driven liquid lithium run steady state and pulsed for a few seconds of high heat flux (˜15MW/m^2) has been used to investigate the transient reaction of the flowing lithium. A similar tray is scheduled to be tested in HT-7, Hefei, China as a limiter in Sept. 2012. Related movies and analysis will be shown.

Lithium-Metal Infused Trenches: Progress toward a Divertor Solution

NASA Astrophysics Data System (ADS)

Ruzic, D. N.; Fiflis, P.; Christenson, M.; Szott, M.; Xu, W.; Jung, S.; Morgan, T. W.; Kalathiparambil, K.

2014-10-01

The application of liquid metal, especially liquid lithium, as a plasma facing component (PFC) has the capacity to offer a strong alternative to solid PFCs by reducing damage concerns and enhancing plasma performance. The Liquid-Metal Infused Trenches (LiMIT) concept is a liquid metal divertor alternative which employs thermoelectric current from either plasma or external heating in tandem with the toroidal field to self-propel liquid lithium through a series of trenches. LiMIT has been tested in several devices, namely HT-7, the UIUC SLiDE and TELS facilities and Magnum PSI at heat fluxes of up to 3 MW/m-2. Results of these experiments, including velocity and temperature measurements, power handling considerations, and preliminary vapor shielding results will be discussed, focusing on the 117 shots performed at Magnum scanning magnetic fields and heat fluxes up to ~ 0.3 T and 3 MW/m-2. Concerns over tritium retention and MHD droplet ejection will additionally be addressed. LiMIT has also been proposed to function as a limiter on the EAST moveable limiter arm and tests have been performed with a prototype module inclined at various angles.

Electromagnetic Pumps for Conductive-Propellant Feed Systems

NASA Technical Reports Server (NTRS)

Markusic, Thomas E.; Polzin, Kurt A.; Dehoyos, Amado

2005-01-01

Prototype electromagnetic pumps for use with lithium and bismuth propellants were constructed and tested. Such pumps may be used to pressurize future electric propulsion liquid metal feed systems, with the primary advantages being the compactness and simplicity versus alternative pressurization technologies. Design details for two different pumps are described: the first was designed to withstand (highly corrosive) lithium propellant, and t he second was designed to tolerate the high temperature required to pump liquid bismuth. Both qualitative and quantitative test results are presented. Open-loop tests demonstrated the capability of each device to electromagnetically pump its design propellant (lithium or bismuth). A second set of tests accurately quantified the pump pressure developed as a function of current. These experiments, which utilized a more easily handled material (gallium), demonstrated continuously-adjustable pump pressure levels ranging from 0-100 Torr for corresponding input current levels of 0-75 A. While the analysis and testing in this study specifically targeted lithium and bismuth propellants, the underlying design principles should be useful in implementing liquid metal pumps in any conductive-propellant feed system.

A molecular dynamics study of lithium-containing aprotic heterocyclic ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Lourenço, Tuanan C.; Zhang, Yong; Costa, Luciano T.; Maginn, Edward J.

2018-05-01

Classical molecular dynamics simulations were performed on twelve different ionic liquids containing aprotic heterocyclic anions doped with Li+. These ionic liquids have been shown to be promising electrolytes for lithium ion batteries. Self-diffusivities, lithium transference numbers, densities, and free volumes were computed as a function of lithium concentration. The dynamics and free volume decreased with increasing lithium concentration, and the trends were rationalized by examining the changes to the liquid structure. Of those examined in the present work, it was found that (methyloxymethyl)triethylphosphonium triazolide ionic liquids have the overall best performance.

Measurements of impurity concentrations and transport in the Lithium Tokamak Experiment

NASA Astrophysics Data System (ADS)

Boyle, D. P.; Bell, R. E.; Kaita, R.; Lucia, M.; Schmitt, J. C.; Scotti, F.; Kubota, S.; Hansen, C.; Biewer, T. M.; Gray, T. K.

2016-10-01

The Lithium Tokamak Experiment (LTX) is a modest-sized spherical tokamak with all-metal plasma facing components (PFCs), uniquely capable of operating with large area solid and/or liquid lithium coatings essentially surrounding the entire plasma. This work presents measurements of core plasma impurity concentrations and transport in LTX. In discharges with solid Li coatings, volume averaged impurity concentrations were low but non-negligible, with 2 - 4 % Li, 0.6 - 2 % C, 0.4 - 0.7 % O, and Zeff < 1.2 . Transport was assessed using the TRANSP, NCLASS, and MIST codes. Collisions with the main H ions dominated the neoclassical impurity transport, and neoclassical transport coefficients calculated with NCLASS were similar across all impurity species and differed no more than a factor of two. However, time-independent simulations with MIST indicated that neoclassical theory did not fully capture the impurity transport and anomalous transport likely played a significant role in determining impurity profiles. Progress on additional analysis, including time-dependent impurity transport simulations and impurity measurements with liquid lithium coatings, and plans for diagnostic upgrades and future experiments in LTX- β will also be presented. This work supported by US DOE contracts DE-AC02-09CH11466 and DE-AC05-00OR22725.

Electrodeposition of Metals in Microgravity Conditions

NASA Technical Reports Server (NTRS)

Nishikawa, K.; Homma, T.; Chassaing, E.; Rosso, M.; Fukunaka, Y.

2012-01-01

Metal electrodeposition may introduce various morphological variations depending on the electrolytic conditions including cell configurations. For liquid electrolytes, a precise study of these deposits may be complicated by convective motion due to buoyancy. Zero-gravity (0-G) condition provided by drop shaft or parabolic flight gives a straightforward mean to avoid this effect: we present here 0-G electrodeposition experiments, which we compare to ground experiments (1-G). Two electrochemical systems were studied by laser interferometry, allowing to measure the concentration variations in the electrolyte: copper deposition from copper sulfate aqueous solution and lithium deposition from an ionic liquid containing LiTFSI. For copper, concentration variations were in good agreement with theory. For lithium, an apparent induction time was observed for the concentration evolution at 1-G: due to this induction time and to the low diffusion coefficient in ionic liquid, the concentration variations were hardly measurable in the parabolic flight 0-G periods of 20 seconds.

Design and Modeling of a Liquid Lithium LiMIT Loop

NASA Astrophysics Data System (ADS)

Szott, Matthew; Christenson, Michael; Stemmley, Steven; Ahn, Chisung; Andruczyk, Daniel; Ruzic, David

2017-10-01

The use of flowing liquid lithium in plasma facing components has been shown to reduce erosion and thermal stress damage, prolong device lifetime, decrease edge recycling, reduce impurities, and increase plasma performance, all while providing a clean and self-healing surface. The Liquid Metal Infused Trench (LiMIT) system has proven the concept of controlled thermoelectric magnetohydrodynamic-driven lithium flow for use in fusion relevant conditions, through tests at UIUC, HT-7, and Magnum PSI. As the use of liquid lithium in fusion devices progresses, emphasis must now be placed on full systems integration of flowing liquid metal concepts. The LiMIT system will be upgraded to include a full liquid lithium loop, which will pump lithium into the fusion device, utilize TEMHD to drive lithium through the vessel, and remove lithium for filtration and degassing. Flow control concepts recently developed at UIUC - including wetting control, dryout control, and flow velocity control - will be tested in conjunction in order to demonstrate a robust system. Lithium loop system requirements, designs, and modeling work will be presented, along with plans for installation and testing on the HIDRA device at UIUC. This work is supported by DOE/ALPS DE-FG02-99ER54515.

Safety and diagnostic systems on the Liquid Lithium Test Stand (LLTS)

NASA Astrophysics Data System (ADS)

Schwartz, J. A.; Jaworski, M. A.; Ellis, R.; Kaita, R.; Mozulay, R.

2013-10-01

The Liquid Lithium Test Stand (LLTS) is a test bed for development of flowing liquid lithium systems for plasma-facing components at PPPL. LLTS is designed to test operation of liquid lithium under vacuum, including flowing, solidifying (such as would be the case at the end of plasma operations), and re-melting. Constructed of stainless steel, LLTS is a closed loop of pipe with two reservoirs and a pump, as well as diagnostics for temperature, flow rate, and pressure. Since liquid lithium is a highly reactive material, special care must be taken when designing such a system. These include a permanent-magnet MHD pump and MHD flow meter that have no mechanical components in direct contact with the liquid lithium. The LLTS also includes an expandable 24-channel leak-detector interlock system which cuts power to heaters and the pump if any lithium leaks from a pipe joint. Design for the interlock systems and flow meter are presented. This work is supported by US DOE Contract DE-AC02-09CH11466.

Experiments and numerical modeling of fast flowing liquid metal thin films under spatially varying magnetic field conditions

NASA Astrophysics Data System (ADS)

Narula, Manmeet Singh

Innovative concepts using fast flowing thin films of liquid metals (like lithium) have been proposed for the protection of the divertor surface in magnetic fusion devices. However, concerns exist about the possibility of establishing the required flow of liquid metal thin films because of the presence of strong magnetic fields which can cause flow disrupting MHD effects. A plan is underway to design liquid lithium based divertor protection concepts for NSTX, a small spherical torus experiment at Princeton. Of these, a promising concept is the use of modularized fast flowing liquid lithium film zones, as the divertor (called the NSTX liquid surface module concept or NSTX LSM). The dynamic response of the liquid metal film flow in a spatially varying magnetic field configuration is still unknown and it is suspected that some unpredicted effects might be lurking. The primary goal of the research work being reported in this dissertation is to provide qualitative and quantitative information on the liquid metal film flow dynamics under spatially varying magnetic field conditions, typical of the divertor region of a magnetic fusion device. The liquid metal film flow dynamics have been studied through a synergic experimental and numerical modeling effort. The Magneto Thermofluid Omnibus Research (MTOR) facility at UCLA has been used to design several experiments to study the MHD interaction of liquid gallium films under a scaled NSTX outboard divertor magnetic field environment. A 3D multi-material, free surface MHD modeling capability is under development in collaboration with HyPerComp Inc., an SBIR vendor. This numerical code called HIMAG provides a unique capability to model the equations of incompressible MHD with a free surface. Some parts of this modeling capability have been developed in this research work, in the form of subroutines for HIMAG. Extensive code debugging and benchmarking exercise has also been carried out. Finally, HIMAG has been used to study the MHD interaction of fast flowing liquid metal films under various divertor relevant magnetic field configurations through numerical modeling exercises.

Liquid-metal plasma-facing component research on the National Spherical Torus Experiment

NASA Astrophysics Data System (ADS)

Jaworski, M. A.; Khodak, A.; Kaita, R.

2013-12-01

Liquid metal plasma-facing components (PFCs) have been proposed as a means of solving several problems facing the creation of economically viable fusion power reactors. Liquid metals face critical issues in three key areas: free-surface stability, material migration and demonstration of integrated scenarios. To date, few demonstrations exist of this approach in a diverted tokamak and we here provide an overview of such work on the National Spherical Torus Experiment (NSTX). The liquid lithium divertor (LLD) was installed and operated for the 2010 run campaign using evaporated coatings as the filling method. Despite a nominal liquid level exceeding the capillary structure and peak current densities into the PFCs exceeding 100 kA m-2, no macroscopic ejection events were observed. The stability can be understood from a Rayleigh-Taylor instability analysis. Capillary restraint and thermal-hydraulic considerations lead to a proposed liquid-metal PFCs scheme of actively-supplied, capillary-restrained systems. Even with state-of-the-art cooling techniques, design studies indicate that the surface temperature with divertor-relevant heat fluxes will still reach temperatures above 700 °C. At this point, one would expect significant vapor production from a liquid leading to a continuously vapor-shielded regime. Such high-temperature liquid lithium PFCs may be possible on the basis of momentum-balance arguments.

Li Experiments at the Tokamak T-11M Toward PFC Concept of Steady State Tokamak-Reactor

NASA Astrophysics Data System (ADS)

Mirnov, S. V.

2009-11-01

As practical method of using a liquid lithium as a renewable plasma-facing component (PCF) for steady state tokamak-reactor the concept of lithium emitter-collector is considered [1]. It is based on lithium filled capillary porous system proposed by V.A. Evtikhin et al. (1996). The lithium circulation process consists of four steps: (1) Li emission from the PFC emitter into the plasma; (2) plasma boundary cooling by non-coronal Li radiation; (3) Li ion capture by the collector (before they are lost to the tokamak chamber wall); (4) Li return from the collector to the emitter. T-11M tokamak experiments have used three local rail limiters made from lithium, molybdenum and graphite as lithium collectors. The lithium behavior was studied by analysis of the witness samples, and by a mobile graphite probe. The key findings are: (1) lithium collection on the ion side of the lithium limiter is 2-3 times larger than on the electron side; (2) total efficiency of Li collection integrated over all three rail limiters can reach 50-70% of the lithium emission during the discharge pulse, while the theoretical limit is about 90%. [1] S.V. Mirnov, J. Nucl. Mat., 390-391, 876 (2009).

Lithium purification technique

DOEpatents

Keough, Robert F.; Meadows, George E.

1985-01-01

A method for purifying liquid lithium to remove unwanted quantities of nitrogen or aluminum. The method involves precipitation of aluminum nitride by adding a reagent to the liquid lithium. The reagent will be either nitrogen or aluminum in a quantity adequate to react with the unwanted quantity of the impurity to form insoluble aluminum nitride. The aluminum nitride can be mechanically separated from the molten liquid lithium.

Lithium purification technique

DOEpatents

Keough, R.F.; Meadows, G.E.

1984-01-10

A method for purifying liquid lithium to remove unwanted quantities of nitrogen or aluminum. The method involves precipitation of aluminum nitride by adding a reagent to the liquid lithium. The reagent will be either nitrogen or aluminum in a quantity adequate to react with the unwanted quantity of the impurity to form insoluble aluminum nitride. The aluminum nitride can be mechanically separated from the molten liquid lithium.

Understanding and improving lithium ion batteries through mathematical modeling and experiments

NASA Astrophysics Data System (ADS)

Deshpande, Rutooj D.

There is an intense, worldwide effort to develop durable lithium ion batteries with high energy and power densities for a wide range of applications, including electric and hybrid electric vehicles. For improvement of battery technology understanding the capacity fading mechanism in batteries is of utmost importance. Novel electrode material and improved electrode designs are needed for high energy- high power batteries with less capacity fading. Furthermore, for applications such as automotive applications, precise cycle-life prediction of batteries is necessary. One of the critical challenges in advancing lithium ion battery technologies is fracture and decrepitation of the electrodes as a result of lithium diffusion during charging and discharging operations. When lithium is inserted in either the positive or negative electrode, there is a volume change associated with insertion or de-insertion. Diffusion-induced stresses (DISs) can therefore cause the nucleation and growth of cracks, leading to mechanical degradation of the batteries. With different mathematical models we studied the behavior of diffusion induces stresses and effects of electrode shape, size, concentration dependent material properties, pre-existing cracks, phase transformations, operating conditions etc. on the diffusion induced stresses. Thus we develop tools to guide the design of the electrode material with better mechanical stability for durable batteries. Along with mechanical degradation, chemical degradation of batteries also plays an important role in deciding battery cycle life. The instability of commonly employed electrolytes results in solid electrolyte interphase (SEI) formation. Although SEI formation contributes to irreversible capacity loss, the SEI layer is necessary, as it passivates the electrode-electrolyte interface from further solvent decomposition. SEI layer and diffusion induced stresses are inter-dependent and affect each-other. We study coupled chemical-mechanical degradation of electrode materials to understand the capacity fading of the battery with cycling. With the understanding of chemical and mechanical degradation, we develop a simple phenomenological model to predict battery life. On the experimental part we come up with a novel concept of using liquid metal alloy as a self-healing battery electrode. We develop a method to prepare thin film liquid gallium electrode on a conductive substrate. This enabled us to perform a series of electrochemical and characterization experiments which certify that liquid electrode undergo liquid-solid-liquid transition and thus self-heals the cracks formed during de-insertion. Thus the mechanical degradation can be avoided. We also perform ab-initio calculations to understand the equilibrium potential of various lithium-gallium phases. KEYWORDS: Lithium ion batteries, diffusion induced stresses, self-healing electrode, coupled chemical and mechanical degradation, life-prediction model.

Mirror plasma apparatus

DOEpatents

Moir, Ralph W.

1981-01-01

A mirror plasma apparatus which utilizes shielding by arc discharge to form a blanket plasma and lithium walls to reduce neutron damage to the wall of the apparatus. An embodiment involves a rotating liquid lithium blanket for a tandem mirror plasma apparatus wherein the first wall of the central mirror cell is made of liquid lithium which is spun with angular velocity great enough to keep the liquid lithium against the first material wall, a blanket plasma preventing the lithium vapor from contaminating the plasma.

Lithium insertion in graphite from ternary ionic liquid-lithium salt electrolytes. I. Electrochemical characterization of the electrolytes

NASA Astrophysics Data System (ADS)

Appetecchi, Giovanni B.; Montanino, Maria; Balducci, Andrea; Lux, Simon F.; Winterb, Martin; Passerini, Stefano

In this paper we report the results of chemical-physical investigation performed on ternary room temperature ionic liquid-lithium salt mixtures as electrolytes for lithium-ion battery systems. The ternary electrolytes were made by mixing N-methyl- N-propyl pyrrolidinium bis(fluorosulfonyl) imide (PYR 13FSI) and N-butyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR 14TFSI) ionic liquids with lithium hexafluorophosphate (LiPF 6) or lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The mixtures were developed based on preliminary results on the cyclability of graphite electrodes in the IL-LiX binary electrolytes. The results clearly show the beneficial synergic effect of the two ionic liquids on the electrochemical properties of the mixtures.

Demonstration of a high-intensity neutron source based on a liquid-lithium target for Accelerator based Boron Neutron Capture Therapy.

PubMed

Halfon, S; Arenshtam, A; Kijel, D; Paul, M; Weissman, L; Berkovits, D; Eliyahu, I; Feinberg, G; Kreisel, A; Mardor, I; Shimel, G; Shor, A; Silverman, I; Tessler, M

2015-12-01

A free surface liquid-lithium jet target is operating routinely at Soreq Applied Research Accelerator Facility (SARAF), bombarded with a ~1.91 MeV, ~1.2 mA continuous-wave narrow proton beam. The experiments demonstrate the liquid lithium target (LiLiT) capability to constitute an intense source of epithermal neutrons, for Accelerator based Boron Neutron Capture Therapy (BNCT). The target dissipates extremely high ion beam power densities (>3 kW/cm(2), >0.5 MW/cm(3)) for long periods of time, while maintaining stable conditions and localized residual activity. LiLiT generates ~3×10(10) n/s, which is more than one order of magnitude larger than conventional (7)Li(p,n)-based near threshold neutron sources. A shield and moderator assembly for BNCT, with LiLiT irradiated with protons at 1.91 MeV, was designed based on Monte Carlo (MCNP) simulations of BNCT-doses produced in a phantom. According to these simulations it was found that a ~15 mA near threshold proton current will apply the therapeutic doses in ~1h treatment duration. According to our present results, such high current beams can be dissipated in a liquid-lithium target, hence the target design is readily applicable for accelerator-based BNCT. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Operational Characteristics of Liquid Lithium Divertor in NSTX

NASA Astrophysics Data System (ADS)

Kaita, R.; Kugel, H.; Abrams, T.; Bell, M. G.; Bell, R. E.; Gerhardt, S.; Jaworski, M. A.; Kallman, J.; Leblanc, B.; Mansfield, D.; Mueller, D.; Paul, S.; Roquemore, A. L.; Scotti, F.; Skinner, C. H.; Timberlake, J.; Zakharov, L.; Maingi, R.; Nygren, R.; Raman, R.; Sabbagh, S.; Soukhanovskii, V.

2010-11-01

Lithium coatings on plasma-facing components (PFC's) have resulted in improved plasma performance on NSTX in deuterium H-mode plasmas with neutral beam heating.^ Salient results included improved electron confinement and ELM suppression. In CDX-U, the use of lithium-coated PFC's and a large-area liquid lithium limiter resulted in a six-fold increase in global energy confinement time. A Liquid Lithium Divertor (LLD) has been installed in NSTX for the 2010 run campaign. The LLD PFC consists of a thin film of lithium on a temperature-controlled substrate to keep the lithium liquefied between shots, and handle heat loads during plasmas. This capability was demonstrated when the LLD withstood a strike point on its surface during discharges with up to 4 MW of neutral beam heating.

Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

PubMed Central

Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

2016-01-01

We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

Atomistic Simulation and Electronic Structure of Lithium Doped Ionic Liquids: Structure, Transport, and Electrochemical Stability

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bauschlicher, Charles W.; Lawson, John W.

2015-01-01

Zero-temperature density functional theory (DFT), density functional theory molecular dynamics (DFT-MD), and classical molecular dynamics using polarizable force fields (PFF-MD) are employed to evaluate the influence of Lithium ion on the structure, transport, and electrochemical stability of three potential ionic liquid electrolytes: N--methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([pyr14][TFSI]), N--methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ([pyr13][FSI]), and 1-ethyl-3--methylimidazolium boron tetrafluoride ([EMIM][BF4]). We characterize the Lithium ion solvation shell through zero-temperature DFT simulations of [Li(Anion)sub n](exp n-1) -clusters, DFT-MD simulations of isolated lithium ions in small ionic liquid systems, and PFF-MD simulations with high Li-doping levels in large ionic liquid systems. At low levels of Li-salt doping, highly stable solvation shells having 2-3 anions are seen in both [pyr14][TFSI] and [pyr13][FSI], while solvation shells with 4 anions dominate in [EMIM][BF sub 4]. At higher levels of doping, we find the formation of complex Li-network structures that increase the frequency of 4 anion-coordinated solvation shells. A comparison of computational and experimental Raman spectra for a wide range of [Li(Anion) sub n](exp n -1) - clusters shows that our proposed structures are consistent with experiment. We estimate the ion diffusion coefficients and quantify both size and simulation time effects. We find estimates of lithium ion diffusion are a reasonable order of magnitude and can be corrected for simulation time effects. Simulation size, on the other hand, is also important, with diffusion coefficients from long PFF-MD simulations of small cells having 20-40% error compared to large-cell values. Finally, we compute the electrochemical window using differences in electronic energy levels of both isolated cation/anion pairs and small ionic liquid systems with Li-salt doping. The single pair and liquid-phase systems provide similar estimates of electrochemical window, while Li-doping in the liquid-phase systems results in electrochemical windows little changed from the neat systems. Pure and hybrid functionals systematically provide an upper and lower bound, respectively, to the experimental electrochemical window for the systems studied here.

Compatibility of AlN with liquid lithium

NASA Astrophysics Data System (ADS)

Terai, T.; Suzuki, A.; Yoneoka, T.; Mitsuyama, T.

2000-12-01

Development of ceramic coatings is one of the most important subjects in liquid blanket research and development. Compatibility of sintered AlN and AlN coatings with liquid lithium, a candidate breeding material, was investigated. Sintered AlN with or without the sintering aid of Y 2O 3 examined in lithium at 773 K for 1390 h showed a slight decrease in electrical resistivity because of a reduction in Al 2O 3 impurity, though AlN and Y 2O 3 components themselves were subject to no severe corrosion. On the other hand, AlN ceramic coatings on SUS430 with high resistivity (> 10 11 Ω m) fabricated by the RF sputtering method disappeared in liquid lithium at 773 K in 56 h. This may be because cracks were formed due to the difference in thermal expansion between the coatings and the substrate or because the oxide formed between the two was removed by liquid lithium.

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

Ruzic, David N.; Andruczyk, Daniel

The implementation of the liquid Lithium Divertor (LLD) in NSTX presented a unique opportunity in plasma-material interactions studies. A high density Langmuir Probe (HDLP) array utilizing a dense pack of triple Langmuir probes was built at PPPL and the electronics designed and built by UIUC. It was shown that the HDLP array could be used to characterize the modification of the EEDF during lithium experiments on NSTX as well as characterize the transient particle loads during lithium experiments as a means to study ELMs. With NSTX being upgraded and a new divertor being installed, the HDLP array will not bemore » used in NSTX-U. However UIUC is currently helping to develop two new systems for depositing lithium into NSTX-U, a Liquid Lithium Pellet Dripper (LLPD) for use with the granular injector for ELM mitigation and control studies as well as an Upward-Facing Lithium Evaporator (U-LITER) based on a flash evaporation system using an electron beam. Currently UIUC has Daniel Andruczyk Stationed at PPPL and is developing these systems as well as being involved in preparing the Materials Analysis Particle Probe (MAPP) for use in LTX and NSTX-U. To date the MAPP preparations have been completed. New sample holders were designed by UIUC?s Research Engineer at PPPL and manufactured at PPPL and installed. MAPP is currently being used on LTX to do calibration and initial studies. The LLPD has demonstrated that it can produce pellets. There is still some adjustments needed to control the frequency and particle size. Equipment for the U-LITER has arrived and initial test are being made of the electron beam and design of the U-LITER in progress. It is expected to have these ready for the first run campaign of NSTX-U.« less

Note: Proton irradiation at kilowatt-power and neutron production from a free-surface liquid-lithium target

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

Halfon, S.; Feinberg, G.; Racah Institute of Physics, Hebrew University, Jerusalem 91904

2014-05-15

The free-surface Liquid-Lithium Target, recently developed at Soreq Applied Research Accelerator Facility (SARAF), was successfully used with a 1.9 MeV, 1.2 mA (2.3 kW) continuous-wave proton beam. Neutrons (∼2 × 10{sup 10} n/s having a peak energy of ∼27 keV) from the {sup 7}Li(p,n){sup 7}Be reaction were detected with a fission-chamber detector and by gold activation targets positioned in the forward direction. The setup is being used for nuclear astrophysics experiments to study neutron-induced reactions at stellar energies and to demonstrate the feasibility of accelerator-based boron neutron capture therapy.

Influence of Polar Organic Solvents in an Ionic Liquid Containing Lithium Bis(fluorosulfonyl)amide: Effect on the Cation-Anion Interaction, Lithium Ion Battery Performance, and Solid Electrolyte Interphase.

PubMed

Lahiri, Abhishek; Li, Guozhu; Olschewski, Mark; Endres, Frank

2016-12-14

Ionic liquid-organic solvent mixtures have recently been investigated as potential battery electrolytes. However, contradictory results with these mixtures have been shown for battery performance. In this manuscript, we studied the influence of the addition of polar organic solvents into the ionic liquid electrolyte 1 M lithium bis(fluorosulfonyl)amide (LiFSI)-1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide ([Py 1,4 ]FSI) and tested it for lithium ion battery applications. From infrared and Raman spectroscopy, clear changes in the lithium solvation and cation-anion interactions in the ionic liquid were observed on addition of organic solvents. From the lithiation/delithiation studies on electrodeposited Ge, the storage capacity for the ionic liquid-highly polar organic solvent (acetonitrile) mixture was found to be the highest at low C-rates (0.425 C) compared to using an ionic liquid alone and ionic liquid-less polar solvent (dimethyl carbonate) mixtures. Furthermore, XPS and AFM were used to evaluate the solid electrolyte interphase (SEI) and to correlate its stability with Li storage capacity.

Protection of tokamak plasma facing components by a capillary porous system with lithium

NASA Astrophysics Data System (ADS)

Lyublinski, I.; Vertkov, A.; Mirnov, S.; Lazarev, V.

2015-08-01

Development of plasma facing material (PFM) based on the Capillary-Porous System (CPS) with lithium and activity on realization of lithium application strategy are addressed to meet the challenges under the creation of steady-state tokamak fusion reactor and fusion neutron source. Presented overview of experimental study of lithium CPS in plasma devices demonstrates the progress in protection of tokamak plasma facing components (PFC) from damage, stabilization and self-renewal of liquid lithium surface, elimination of plasma pollution and lithium accumulation in tokamak chamber. The possibility of PFC protection from the high power load related to cooling of the tokamak boundary plasma by radiation of non-fully stripped lithium ions supported by experimental results. This approach demonstrated in scheme of closed loops of Li circulation in the tokamak vacuum chamber and realized in a series of design of tokamak in-vessel elements.

Particle control and plasma performance in the Lithium Tokamak eXperimenta)

NASA Astrophysics Data System (ADS)

Majeski, R.; Abrams, T.; Boyle, D.; Granstedt, E.; Hare, J.; Jacobson, C. M.; Kaita, R.; Kozub, T.; LeBlanc, B.; Lundberg, D. P.; Lucia, M.; Merino, E.; Schmitt, J.; Stotler, D.; Biewer, T. M.; Canik, J. M.; Gray, T. K.; Maingi, R.; McLean, A. G.; Kubota, S.; Peebles, W. A.; Beiersdorfer, P.; Clementson, J. H. T.; Tritz, K.

2013-05-01

The Lithium Tokamak eXperiment is a small, low aspect ratio tokamak [Majeski et al., Nucl. Fusion 49, 055014 (2009)], which is fitted with a stainless steel-clad copper liner, conformal to the last closed flux surface. The liner can be heated to 350 °C. Several gas fueling systems, including supersonic gas injection and molecular cluster injection, have been studied and produce fueling efficiencies up to 35%. Discharges are strongly affected by wall conditioning. Discharges without lithium wall coatings are limited to plasma currents of order 10 kA, and discharge durations of order 5 ms. With solid lithium coatings discharge currents exceed 70 kA, and discharge durations exceed 30 ms. Heating the lithium wall coating, however, results in a prompt degradation of the discharge, at the melting point of lithium. These results suggest that the simplest approach to implementing liquid lithium walls in a tokamak—thin, evaporated, liquefied coatings of lithium—does not produce an adequately clean surface.

Design and Development of the Liquid Lithium Limiter (L3) for CDX-U

NASA Astrophysics Data System (ADS)

Seraydarian, R. P.; Chousal, L.; Doerner, R. P.; Luckhardt, S. C.; Lynch, T.

2000-10-01

--- This poster describes experiments with liquid Li that informed the design of a Liquid Lithium Limter (L3) built by UCSD for installation on the CDX-U spherical torus at PPPL. It was necessary to resort to wetting liquid Li to textured structures in order for the limiter to intercept 2-3 density e-folding lengths of the scrape off layer (3 cm) of the CDX-U plasma. Since Li is chemically active and corrodes rapidly in all but the driest air, we carried out wetting experiments in vacuum (10-7 - 10-8 torr) and also in Ar at near atmospheric pressure. Wetting of steel occurred reliably at substrate temperatures near 500 ^oC under all conditions, but this high temperature presented special problems of rapid material loss through evaporation, especially under vacuum. Once the surface is wetted, however, lost Li can be replenished at ~ 200 ^oC (just above the melting temperature) where evaporation is negligible. A wetted limiter can even be cooled to room temperature and then reheated many hours later as long as clean conditions are maintained. Surface textures, heating techniques, effective seal materials for piston-driven liquid Li reservoirs, and other aspects of the limiter system design will be presented. Work supported by US DOE grant DE-FG03-95ER54301

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C.A.; Xu, K.; Liu, C.

1996-01-16

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100 C or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors. 4 figs.

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C. Austen; Xu, Kang; Liu, Changle

1996-01-01

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors.

Optimized Wavelength-Tuned Nonlinear Frequency Conversion Using a Liquid Crystal Clad Waveguide

NASA Technical Reports Server (NTRS)

Stephen, Mark A. (Inventor)

2018-01-01

An optimized wavelength-tuned nonlinear frequency conversion process using a liquid crystal clad waveguide. The process includes implanting ions on a top surface of a lithium niobate crystal to form an ion implanted lithium niobate layer. The process also includes utilizing a tunable refractive index of a liquid crystal to rapidly change an effective index of the lithium niobate crystal.

The Effects of Temperature and Oxidation on Deuterium Retention in Solid and Liquid Lithium Films on Molybdenum Plasma-Facing Components

NASA Astrophysics Data System (ADS)

Capece, Angela

2014-10-01

Liquid metal plasma-facing components (PFCs) enable in-situ renewal of the surface, thereby offering a solution to neutron damage, erosion, and thermal fatigue experienced by solid PFCs. Lithium in particular has a high chemical affinity for hydrogen, which has resulted in reduced recycling and enhanced plasma performance on many fusion devices including TFTR, T11-M, FTU, CDX-U, LTX, TJ-II, and NSTX. A key component to the improvement in plasma performance is deuterium retention in Li; however, this process is not well understood in the complex tokamak environment. Recent surface science experiments conducted at the Princeton Plasma Physics Laboratory have used electron spectroscopy and temperature programmed desorption to understand the mechanisms for D retention in Li coatings on Mo substrates. The experiments were designed to give monolayer-control of Li films and were conducted in ultrahigh vacuum under controlled environments. An electron cyclotron resonance plasma source was used to deliver a beam of deuterium ions to the surface over a range of ion energies. Our work shows that D is retained as LiD in metallic Li films. However, when oxygen is present in the film, either by diffusion from the subsurface at high temperature or as a contaminant during the deposition process, Li oxides are formed that retain D as LiOD. Experiments indicate that LiD is more thermally stable than LiOD, which decomposes to liberate D2 gas and D2O at temperatures 100 K lower than the LiD decomposition temperature. Other experiments show how D retention varies with substrate temperature to provide insight into the differences between solid and liquid lithium films. This work was supported by DOE Contract No. DE AC02-09CH11466.

Mapping the Free Energy of Lithium Solvation in the Protic Ionic Liquid Ethylammonuim Nitrate: A Metadynamics Study.

PubMed

Kachmar, Ali; Carignano, Marcelo; Laino, Teodoro; Iannuzzi, Marcella; Hutter, Jürg

2017-08-10

Understanding lithium solvation and transport in ionic liquids is important due to their possible application in electrochemical devices. Using first-principles simulations aided by a metadynamics approach we study the free-energy landscape for lithium ions at infinite dilution in ethylammonium nitrate, a protic ionic liquid. We analyze the local structure of the liquid around the lithium cation and obtain a quantitative picture in agreement with experimental findings. Our simulations show that the lowest two free energy minima correspond to conformations with the lithium ion being solvated either by three or four nitrate ions with a transition barrier between them of 0.2 eV. Other less probable conformations having different solvation pattern are also investigated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acquisition of Co metal from spent lithium-ion battery using emulsion liquid membrane technology and emulsion stability test

NASA Astrophysics Data System (ADS)

Yuliusman; Wulandari, P. T.; Amiliana, R. A.; Huda, M.; Kusumadewi, F. A.

2018-03-01

Lithium-ion batteries are the most common type to be used as energy source in mobile phone. The amount of lithium-ion battery wastes is approximated by 200 – 500 ton/year. In one lithium-ion battery, there are 5 – 20% of cobalt metal, depend on the manufacturer. One of the way to recover a valuable metal from waste is leaching process then continued with extraction, which is the aim of this study. Spent lithium-ion batteries will be characterized with EDX and AAS, the result will show the amount of cobalt metal with form of LiCoO2 in the cathode. Hydrochloric acid concentration used is 4 M, temperature 80°C, and reaction time 1 hour. This study will discuss the emulsion stability test on emulsion liquid membrane. The purpose of emulsion stability test in this study was to determine optimum concentration of surfactant and extractant to produce a stable emulsion. Surfactant and extractant used were SPAN 80 and Cyanex 272 respectively with both concentrations varied. Membrane and feed phase ratios used in this experiment was 1 : 2. The optimum results of this study were SPAN 80 concentrations of 10% w/v and Cyanex 272 0.7 M.

Analysis of secondary cells with lithium anodes and immobilized fused-salt electrolytes

NASA Technical Reports Server (NTRS)

Cairns, E. J.; Rogers, G. L.; Shimotake, H.

1969-01-01

Secondary cells with liquid lithium anodes, liquid bismuth or tellurium cathodes, and fused lithium halide electrolytes immobilized as rigid pastes operate between 380 and 485 degrees. Applications include power sources in space, military vehicle propulsion and special commercial vehicle propulsion.

A sealed optical cell for the study of lithium-electrode|electrolyte interfaces

NASA Astrophysics Data System (ADS)

Howlett, P. C.; MacFarlane, D. R.; Hollenkamp, A. F.

A sealed, symmetrical, lithium optical cell, which enables optical images of lithium surface deposits and in situ Raman spectra to be obtained simply and conveniently during charge-discharge cycling of lithium metal electrodes, has been designed and tested. A conventional aprotic liquid, 1 M lithium hexafluorophosphate in propylene carbonate, and an experimental ionic liquid, 20 mol% lithium bis(trifluoromethanesulfonyl)amide in 1-ethyl 3-methyl imidazolium bis(trifluoromethanesulfonyl)amide, are investigated as electrolyte solutions. Images obtained from the cell with the former electrolyte solution demonstrate the problems associated with cycling lithium metal electrodes. Images obtained with the latter electrolyte solution provide clear evidence that continued investigation of ionic liquids for use with lithium metal electrodes is warranted. Operation of the cell with the conventional electrolyte yields Raman spectra of good quality. The spectra display vibrational modes which arise from the electrolyte, as well as several additional modes which are associated with the deposits formed during cycling.

Stabilizing lithium metal using ionic liquids for long-lived batteries

PubMed Central

Basile, A.; Bhatt, A. I.; O'Mullane, A. P.

2016-01-01

Suppressing dendrite formation at lithium metal anodes during cycling is critical for the implementation of future lithium metal-based battery technology. Here we report that it can be achieved via the facile process of immersing the electrodes in ionic liquid electrolytes for a period of time before battery assembly. This creates a durable and lithium ion-permeable solid–electrolyte interphase that allows safe charge–discharge cycling of commercially applicable Li|electrolyte|LiFePO4 batteries for 1,000 cycles with Coulombic efficiencies >99.5%. The tailored solid–electrolyte interphase is prepared using a variety of electrolytes based on the N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide room temperature ionic liquid containing lithium salts. The formation is both time- and lithium salt-dependant, showing dynamic morphology changes, which when optimized prevent dendrite formation and consumption of electrolyte during cycling. This work illustrates that a simple, effective and industrially applicable lithium metal pretreatment process results in a commercially viable cycle life for a lithium metal battery. PMID:27292652

Lithium-Sulfur Batteries: from Liquid to Solid Cells?

DOE PAGES

Lin, Zhan; Liang, Chengdu

2014-11-11

Lithium-sulfur (Li-S) batteries supply a theoretical specific energy 5 times higher than that of lithium-ion batteries (2,500 vs. ~500 Wh kg-1). However, the insulating properties and polysulfide shuttle effects of the sulfur cathode and the safety concerns of the lithium anode in liquid electrolytes are still key limitations to practical use of traditional Li-S batteries. In this review, we start with a brief discussion on fundamentals of Li-S batteries and key challenges associated with the conventional liquid cells. Then, we introduce the most recent progresses in the liquid systems, including the sulfur positive electrodes, the lithium negative electrodes, and themore » electrolytes and binders. We discuss the significance of investigating electrode reaction mechanisms in liquid cells using in-situ techniques to monitor the compositional and morphological changes. By moving from the traditional liquid cells to recent solid cells, we discuss the importance of this game-changing shift with positive advances in both solid electrolytes and electrode materials. Finally, the opportunities and perspectives for future research on Li-S batteries are presented.« less

Ionic Liquid-Doped Gel Polymer Electrolyte for Flexible Lithium-Ion Polymer Batteries

PubMed Central

Zhang, Ruisi; Chen, Yuanfen; Montazami, Reza

2015-01-01

Application of gel polymer electrolytes (GPE) in lithium-ion polymer batteries can address many shortcomings associated with liquid electrolyte lithium-ion batteries. Due to their physical structure, GPEs exhibit lower ion conductivity compared to their liquid counterparts. In this work, we have investigated and report improved ion conductivity in GPEs doped with ionic liquid. Samples containing ionic liquid at a variety of volume percentages (vol %) were characterized for their electrochemical and ionic properties. It is concluded that excess ionic liquid can damage internal structure of the batteries and result in unwanted electrochemical reactions; however, samples containing 40–50 vol % ionic liquid exhibit superior ionic properties and lower internal resistance compared to those containing less or more ionic liquids.

On the role of quantum ion dynamics for the anomalous melting of lithium

NASA Astrophysics Data System (ADS)

Elatresh, Sabri; Bonev, Stanimir

2011-03-01

Lithium has attracted a lot of interest in relation to a number of counterintuitive electronic and structural changes that it exhibits under pressure. One of the most remarkable properties of dense lithium is its anomalous melting. This behavior was first predicted theoretically based on first-principles molecular dynamics (FPMD) simulations, which treated the ions classically. The lowest melting temperature was determined to be about 275~K at 65~GPa. Recent experiments measured a melting temperature about 100~K lower at the same pressure. In this talk, we will present FPMD calculations of solid and liquid lithium free energies up to 100 GPa that take into account ion quantum dynamics. We examine the significance of the quantum effects for the finite-temperature phase boundaries of lithium and, in particular, its melting curve. Work supported by NSERC, Acenet, and LLNL under Contract DE-AC52-07NA27344.

Temperature Dependence of Lithium Reactions with Air

NASA Astrophysics Data System (ADS)

Sherrod, Roman; Skinner, C. H.; Koel, Bruce

2016-10-01

Liquid lithium plasma facing components (PFCs) are being developed to handle long pulse, high heat loads in tokamaks. Wetting by lithium of its container is essential for this application, but can be hindered by lithium oxidation by residual gases or during tokamak maintenance. Lithium PFCs will experience elevated temperatures due to plasma heat flux. This work presents measurements of lithium reactions at elevated temperatures (298-373 K) when exposed to natural air. Cylindrical TZM wells 300 microns deep with 1 cm2 surface area were filled with metallic lithium in a glovebox containing argon with less than 1.6 ppm H20, O2, and N2. The wells were transferred to a hot plate in air, and then removed periodically for mass gain measurements. Changes in the surface topography were recorded with a microscope. The mass gain of the samples at elevated temperatures followed a markedly different behavior to that at room temperature. One sample at 373 K began turning red indicative of lithium nitride, while a second turned white indicative of lithium carbonate formation. Data on the mass gain vs. temperature and associated topographic changes of the surface will be presented. Science Undergraduate Laboratory Internship funded by Department of Energy.

An investigation of voids formation mechanisms and their effects on freeze and thaw processes of lithium and lithium fluoride

NASA Technical Reports Server (NTRS)

El-Genk, Mohamed S.; Yang, Jae-Young

1991-01-01

The mechanisms of void formation during the cooldown and freezing of lithium coolant within the primary loop of SP-100 type systems are investigated. These mechanisms are: (1) homogeneous nucleation; (2) heterogeneous nucleation; (3) normal segregation of helium gas dissolved in liquid lithium; and (4) shrinkage of lithium during freezing. To evaluate the void formation potential due to segregation, a numerical scheme that couples the freezing and mass diffusion processes in both the solid and liquid regions is developed. The results indicated that the formation of He bubbles is unlikely by either homogeneous or heterogeneous nucleation during the cooldown process. However, homogeneous nucleation of He bubbles following the segregation of dissolved He in liquid lithium ahead of the solid-liquid interface is likely to occur. Results also show that total volume of He void is insignificant when compared to that of shrinkage voids. In viewing this, the subsequent research focuses on the effects of shrinkage void forming during freezing of lithium on subsequent thaw processes are investigated using a numerical scheme that is based on a single (solid/liquid) cell approach. The cases of lithium-fluoride are also investigated to show the effect of larger volume shrinkage upon freezing on the freeze and thaw processes. Results show that a void forming at the wall appreciably reduces the solid-liquid interface velocity, during both freeze and thaw, and causes a substantial rise in the wall temperature during thaw. However, in the case of Li, the maximum wall temperature was much lower than the melting temperature of PWC-11, which is used as the structure material in the SP-100 system. Hence, it is included that a formation of hot spots is unlikely during the startup or restart of the SP-100 system.

Study of plasma-facing components in the Lithium Tokamak Experiment with the Materials Analysis and Particle Probe

NASA Astrophysics Data System (ADS)

Lucia, M.; Kaita, R.; Majeski, R.; Boyle, D. P.; Granstedt, E. M.; Jacobson, C. M.; Schmitt, J. C.; Allain, J. P.; Bedoya, F.; Gonderman, S.

2013-10-01

The Lithium Tokamak Experiment (LTX) is a spherical torus designed to accommodate solid or liquid lithium as the primary plasma-facing component (PFC). We present initial results from the implementation on LTX of the Materials Analysis and Particle Probe (MAPP) diagnostic, a collaboration among PPPL, Purdue University, and the University of Illinois. MAPP is a compact in vacuo surface science diagnostic, and its operation on LTX will provide the first ever in situ surface measurements of a tokamak first wall environment. With MAPP's analysis techniques, we will study the evolution of the surface chemistry of LTX's first wall as a function of varied temperature and lithium coating. During its 2013 run campaign, LTX will use an electron beam to evaporate lithium onto the first wall from an in-vessel reservoir. We will use two quartz crystal microbalances to estimate thickness of lithium coatings thus applied to the MAPP probe. We have recently installed a set of triple Langmuir probes on LTX, and they will be used to relate LTX edge plasma parameters to MAPP results. We will combine data from MAPP and the triple probes to estimate the local edge recycling coefficient based on desorption of retained hydrogen. This work was supported by U.S. DOE contract DE-AC02-09CH11466.

High performance batteries with carbon nanomaterials and ionic liquids

DOEpatents

Lu, Wen [Littleton, CO

2012-08-07

The present invention is directed to lithium-ion batteries in general and more particularly to lithium-ion batteries based on aligned graphene ribbon anodes, V.sub.2O.sub.5 graphene ribbon composite cathodes, and ionic liquid electrolytes. The lithium-ion batteries have excellent performance metrics of cell voltages, energy densities, and power densities.

Ionic liquids as electrolytes for Li-ion batteries-An overview of electrochemical studies

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Świderska-Mocek, Agnieszka

The paper reviews properties of room temperature ionic liquids (RTILs) as electrolytes for lithium and lithium-ion batteries. It has been shown that the formation of the solid electrolyte interface (SEI) on the anode surface is critical to the correct operation of secondary lithium-ion batteries, including those working with ionic liquids as electrolytes. The SEI layer may be formed by electrochemical transformation of (i) a molecular additive, (ii) RTIL cations or (iii) RTIL anions. Such properties of RTIL electrolytes as viscosity, conductivity, vapour pressure and lithium-ion transport numbers are also discussed from the point of view of their influence on battery performance.

Ionic Liquids in Lithium-Ion Batteries.

PubMed

Balducci, Andrea

2017-04-01

Lithium-ion batteries are among the most widespread energy storage devices in our society. In order to introduce these devices in new key applications such as transportation, however, their safety and their operative temperature range need to be significantly improved. These improvements can be obtained only by developing new electrolytes. Ionic liquids are presently considered among the most attractive electrolytes for the development of advanced and safer lithium-ion batteries. In this manuscript, the use of various types of ionic liquids, e.g. aprotic and protic, in lithium-ion batteries is considered. The advantages and the limits associated to the use of these innovative electrolytes are critically analysed.

Electrical detection of liquid lithium leaks from pipe joints.

PubMed

Schwartz, J A; Jaworski, M A; Mehl, J; Kaita, R; Mozulay, R

2014-11-01

A test stand for flowing liquid lithium is under construction at Princeton Plasma Physics Laboratory. As liquid lithium reacts with atmospheric gases and water, an electrical interlock system for detecting leaks and safely shutting down the apparatus has been constructed. A defense in depth strategy is taken to minimize the risk and impact of potential leaks. Each demountable joint is diagnosed with a cylindrical copper shell electrically isolated from the loop. By monitoring the electrical resistance between the pipe and the copper shell, a leak of (conductive) liquid lithium can be detected. Any resistance of less than 2 kΩ trips a relay, shutting off power to the heaters and pump. The system has been successfully tested with liquid gallium as a surrogate liquid metal. The circuit features an extensible number of channels to allow for future expansion of the loop. To ease diagnosis of faults, the status of each channel is shown with an analog front panel LED, and monitored and logged digitally by LabVIEW.

Simplified thermochemistry of oxygen in lithium and sodium for liquid metal cooling systems

NASA Technical Reports Server (NTRS)

Tower, L. K.

1972-01-01

Plots of oxygen chemical potential against composition of lithium-oxygen solutions and sodium-oxygen solutions for a range of temperature were constructed. For each liquid metal two such plots were prepared. For one plot ideal solution behavior was assumed. For the other plot, existing solubility limit data for oxygen in the liquid metal were used to determine a first-order term for departure from ideality. The use of the plots in evaluating the oxygen gettering capability of refractory metals in liquid metal cooling systems is illustrated by a simple example involving lithium, oxygen, and hafnium.

Ab initio molecular dynamics simulations of the initial stages of solid-electrolyte interphase formation on lithium ion battery graphitic anodes.

PubMed

Leung, Kevin; Budzien, Joanne L

2010-07-07

The decomposition of ethylene carbonate (EC) during the initial growth of solid-electrolyte interphase (SEI) films at the solvent-graphitic anode interface is critical to lithium ion battery operations. Ab initio molecular dynamics simulations of explicit liquid EC/graphite interfaces are conducted to study these electrochemical reactions. We show that carbon edge terminations are crucial at this stage, and that achievable experimental conditions can lead to surprisingly fast EC breakdown mechanisms, yielding decomposition products seen in experiments but not previously predicted.

Impulsive Stimulated Light Scattering Studies of the Liquid-Glass Transition: on the Experimental Verification of Mode-Coupling Theory Predictions.

NASA Astrophysics Data System (ADS)

Halalay, Ion C.

A study of the structural glass transition trough impulsive stimulated light scattering experiments has been carried out in concentrated aqueous lithium chloride solutions, at temperatures ranging from ambient to cryogenic. A specially designed sample cell made it possible to cover the whole temperature interval from simple liquid, to viscoelastic supercooled liquid, to glass. It is shown that a phenomenological description of the results of these experiments in terms of a spectrum of relaxation times through the use of a Kohlrausch-Williams-Watts relaxation function is inadequate. Based on predictions of mode-coupling theory of the liquid-glass transition, an alternative approach to data interpretation is proposed. It is shown that for an aqueous lithium chloride solution, the prediction of simple scaling and identical scaling for mechanical and electrical susceptibilities seems to be valid. However, another prediction of theory is called into question: instead of a power-law behavior on temperature difference, it is found experimentally that the behavior of the susceptibility spectrum minimum is exponential. Similar disagreements are found for other two materials, triphenyl phosphite and polypropylene oxide. The causes for these discrepancies are discussed and it is concluded that additional experimentation is necessary to verify theoretical claims. Experiments are proposed which can test these predictions and serve as guide for the construction of theoretical models for the glass transition in real systems. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617 -253-5668; Fax 617-253-1690.).

Cycling and rate performance of Li-LiFePO 4 cells in mixed FSI-TFSI room temperature ionic liquids

NASA Astrophysics Data System (ADS)

Lewandowski, A. P.; Hollenkamp, A. F.; Donne, S. W.; Best, A. S.

A study is conducted of the performance of lithium iron(II) phosphate, LiFePO 4, as a cathode material in a lithium secondary battery that features an ionic liquid electrolyte solution and a metallic lithium anode. The electrolyte solution comprises an ionic liquid of a N-methyl-N-alkyl-pyrrolidinium (alkyl = n-propyl or n-butyl) cation and either the bis(fluorosulfonyl)imide [(FSO 2) 2N -] or bis(trifluoromethanesulfonyl)imide [(F 3CSO 2) 2N -] anion, together with 0.5 mol kg -1 of lithium bis(trifluoromethanesulfonyl)imide salt. For N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide, coin cells discharging at rates of C/10 and 4C yield specific capacities of 153 and 110 mAh g -1, respectively, at an average coulombic efficiency of 99.8%. This performance is maintained for over 400 cycles at 50 °C and therefore indicates that these electrolyte solutions support long-term cycling of both LiFePO 4 and metallic lithium while, due to the negligible volatility of ionic liquids, surrounding the lithium in an inherently safe, non-flammable medium.

Investigation Of A Tin-Lithium Alloy As A Liquid Plasma-Facing Material

NASA Astrophysics Data System (ADS)

Sandefur, Heather; Ruzic, David; Kolasinski, Robert; Buchenauer, Dean; Sandia National Laboratories Collaboration; University of Illinois Collaboration

2017-10-01

Sn-Li is a low melting-point alloy that has been identified as a material with favorable performance in plasma material interaction studies. While lithium is a low Z material with a demonstrated ability to absorb impinging ions, pure lithium is plagued by high evaporation rates in the liquid phase. The Sn-Li alloy is a more stable alternative that provides a lower rate of evaporative flux due to the high vapor pressure of tin. In the liquid phase, the bulk segregation of lithium to the surface of the material has also been observed. While the alloy is of considerable interest, little data has been collected on its surface chemistry in a plasma environment. In order to expand the existing body of knowledge in this area, samples of an 80 percent Sn-20 percent Li alloy were prepared and analyzed in order to assess the surface composition and degree of lithium segregation in the liquid phase. The Angle-Resolved Ion Energy Spectrometer (ARIES) at Sandia National Laboratories was used to probe the surfaces of the alloy using the low energy ion scattering method. The lithium coverage at the surface was measured, and the material's affinity for hydrogen chemisorption was investigated.

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

Rock-salt structure lithium deuteride formation in liquid lithium with high-concentrations of deuterium: a first-principles molecular dynamics study

DOE PAGES

Chen, Mohan; Abrams, T.; Jaworski, M. A.; ...

2015-12-17

Because of lithium's possible use as a first wall material in a fusion reactor, a fundamental understanding of the interactions between liquid lithium (Li) and deuterium (D) is important. Here, we predict structural and dynamical properties of liquid Li samples with high concentrations of D, as derived from first-principles molecular dynamics simulations. Liquid Li samples with four concentrations of inserted D atoms (LiDmore » $$_{\\beta}$$ , $$\\beta =0.25$$ , 0.50, 0.75, and 1.00) are studied at temperatures ranging from 470 to 1143 K. Densities, diffusivities, pair distribution functions, bond angle distribution functions, geometries, and charge transfer between Li and D atoms are calculated and analyzed. The analysis suggests liquid–solid phase transitions can occur at some concentrations and temperatures, forming rock-salt LiD within liquid Li. Finally, we observed the formation of some D 2 molecules at high D concentrations.« less

Study of the corrosion behaviors of 304 austenite stainless steel specimens exposed to static liquid lithium at 600 K

NASA Astrophysics Data System (ADS)

Meng, Xiancai; Zuo, Guizhong; Ren, Jun; Xu, Wei; Sun, Zhen; Huang, Ming; Hu, Wangyu; Hu, Jiansheng; Deng, Huiqiu

2016-11-01

Investigation of corrosion behavior of stainless steel served as one kind of structure materials exposed to liquid lithium (Li) is one of the keys to apply liquid Li as potential plasma facing materials (PFM) or blanket coolant in the fusion device. Corrosion experiments of 304 austenite stainless steel (304 SS) were carried out in static liquid Li at 600 K and up to1584 h at high vacuum with pressure less than 4 × 10-4 Pa. After exposure to liquid Li, it was found that the weight of 304 SS slightly decreased with weight loss rate of 5.7 × 10-4 g/m2/h and surface hardness increased by about 50 HV. Lots of spinel-like grains and holes were observed on the surface of specimens measured by SEM. By further EDS, XRD and metallographic analyzing, it was confirmed that the main compositions of spinel-like grains were M23C6 carbides, and 304 SS produced a non-uniform corrosion behavior by preferential grain boundary attack, possibly due to the easy formation of M23C6 carbides and/or formation of Li compound at grain boundaries.

Mixed organic compound-ionic liquid electrolytes for lithium battery electrolyte systems

NASA Astrophysics Data System (ADS)

Montanino, M.; Moreno, M.; Carewska, M.; Maresca, G.; Simonetti, E.; Lo Presti, R.; Alessandrini, F.; Appetecchi, G. B.

2014-12-01

The thermal, transport, rheological and flammability properties of electrolyte mixtures, proposed for safer lithium-ion battery systems, were investigated as a function of the mole composition. The blends were composed of a lithium salt (LiTFSI), organic solvents (namely EC, DEC) and an ionic liquid (PYR13TFSI). The main goal is to combine the fast ion transport properties of the organic compounds with the safe issues of the non-flammable and non-volatile ionic liquids. Preliminary tests in batteries have evidenced cycling performance approaching that observed in commercial organic electrolytes.

Experiments on Condensed Matter Nuclear Events in Kobe University

NASA Astrophysics Data System (ADS)

Minari, T.; Nishio, R.; Taniike, A.; Furuyama, Y.; Kitamura, A.

2006-02-01

We review three kinds of experimental works underway in our laboratory to investigate nuclear events in solid or liquid materials. The largest effort has been given to experiments to confirm the 7Li(d, n2α) reaction rate enhancement reaching 1015 in liquid lithium which was reported by H. Ikegami and R. Pettersson, Evidence of Enhanced Nonthermal Nuclear Fusion (Bulletin of Institute of Chemistry, BENF No. 3, Uppsala University, Sweden, September 2002). Li liquid droplets are formed as targets, and to keep them as pure as possible, we built a liquid Li loop. Thus far, in all cases of irradiation at the temperature from 520 to 570 K with 10-24 keV deuterons, we have not been able to reproduce the Ikegami enhancement for the 7Li(d, n2α) reaction.

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

M. Ono, M. Jaworski, R. Kaita, C. N. Skinner, J.P. Allain, R. Maingi, F. Scotti, V.A. Soukhanovskii, and the NSTX-U Team

Developing a reactor compatible divertor and managing the associated plasma material interaction (PMI) has been identified as a high priority research area for magnetic confinement fusion. Accordingly on NSTXU, the PMI research has received a strong emphasis. With ~ 15 MW of auxiliary heating power, NSTX-U will be able to test the PMI physics with the peak divertor plasma facing component (PFC) heat loads of up to 40-60 MW/m2 . To support the PMI research, a comprehensive set of PMI diagnostic tools are being implemented. The snow-flake configuration can produce exceptionally high divertor flux expansion of up to ~ 50.more » Combined with the radiative divertor concept, the snow-flake configuration has reduced the divertor heat flux by an order of magnitude in NSTX. Another area of active PMI investigation is the effect of divertor lithium coating (both in solid and liquid phases). The overall NSTX lithium PFC coating results suggest exciting opportunities for future magnetic confinement research including significant electron energy confinement improvements, Hmode power threshold reduction, the control of Edge Localized Modes (ELMs), and high heat flux handling. To support the NSTX-U/PPPL PMI research, there are also a number of associated PMI facilities implemented at PPPL/Princeton University including the Liquid Lithium R&D facility, Lithium Tokamak Experiment, and Laboratories for Materials Characterization and Surface Chemistry.« less

Measurement and modeling of surface temperature dynamics of the NSTX liquid lithium divertor

NASA Astrophysics Data System (ADS)

McLean, A. G.; Gan, K. F.; Ahn, J.-W.; Gray, T. K.; Maingi, R.; Abrams, T.; Jaworski, M. A.; Kaita, R.; Kugel, H. W.; Nygren, R. E.; Skinner, C. H.; Soukhanovskii, V. A.

2013-07-01

Dual-band infrared (IR) measurements of the National Spherical Torus eXperiment (NSTX) Liquid Lithium Divertor (LLD) are reported that demonstrate liquid Li is more effective at removing plasma heat flux than Li-conditioned graphite. Extended dwell of the outer strike point (OSP) on the LLD caused an incrementally larger area to be heated above the Li melting point through the discharge leading to enhanced D retention and plasma confinement. Measurement of Tsurface near the OSP demonstrates a significant reduction of the LLD surface temperature compared to that of Li-coated graphite at the same major radius. Modeling of these data with a 2-D simulation of the LLD structure in the DFLUX code suggests that the structure of the LLD was successful at handling up to q⊥,peak = 5 MW/m2 inter-ELM and up to 10 MW/m2 during ELMs from its plasma-facing surface as intended, and provide an innovative method for inferring the Li layer thickness.

Electrochemical Energy Storage Materials

DTIC Science & Technology

2012-07-01

of porous polypropylene membrane (Celgrad® 2400) separators soaked in a liquid electrolyte solution containing 1.0 M lithium hexafluorophosphate ... Lithium Li-ion Lithium ion LiO2 Lithium Dioxide LiOx Lithium Oxide (non stoichiometric) LiPF6 lithium hexafluorophosphate LT-ALD Low Temperature...Nanostructured Battery Architectures, Nanostructured Lithium Ion Batteries 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT: SAR 18. NUMBER OF

Interfacial stability and electrochemical behavior of Li/LiFePO4 batteries using novel soft and weakly adhesive photo-ionogel electrolytes

NASA Astrophysics Data System (ADS)

Aidoud, D.; Etiemble, A.; Guy-Bouyssou, D.; Maire, E.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

2016-10-01

We have developed flexible polymer-gel electrolytes based on a polyacrylate cross-linked matrix that confines an ionic liquid doped with a lithium salt. Free-standing solid electrolyte membrane is obtained after UV photo-polymerization of acrylic monomers dissolved inside the ionic liquid/lithium salt mixture. The liquid precursor of the photo-ionogel may also be directly deposited onto porous composite electrode, which results in all-solid state electrode/electrolyte stacking after UV illumination. Minor variations in the polymer component of the electrolyte formulation significantly affect the electrochemical behavior in LiFePO4/lithium and lithium/lithium cells. The rate performance increases with an increase of the ionic conductivity, which decreases with the polymer content and decreases with increasing oxygen content in the polyacrylate matrix. Their fairly low modulus endow them weak and beneficial pressure-sensitive-adhesive character. X-Rays Tomography shows that the solid-state photo-ionogel electrolytes keep their integrity upon cycling and that their surface remains smooth. The coulombic efficiency of LiFePO4/lithium cells increases with an increase of the adhesive strength of the photo-ionogel, suggesting a relationship between the contact intimacy at the lithium/photo-ionogel interface and the efficiency of the lithium striping/plating. In lithium/lithium cells, only the photo-ionogels with the higher adhesion strength are able to allow the reversible striping/plating of lithium.

Dynamics and lithium binding energies of polyelectrolytes based on functionalized poly(para-phenylene terephthalamide).

PubMed

Grozema, F C; Best, A S; van Eijck, L; Stride, J; Kearley, G J; de Leeuw, S W; Picken, S J

2005-04-28

Polyelectrolyte materials are an interesting class of electrolytes for use in fuel cell and battery applications. Poly(para-phenylene terephthalamide) (PPTA, Kevlar) is a liquid crystalline polymer that, when sulfonated, is a polyelectrolyte that exhibits moderate ion conductivity at elevated temperatures. In this work, quasi-elastic neutron scattering (QENS) experiments were performed to gain insight into the effect of the presence of lithium counterions on the chain dynamics in the material. It was found that the addition of lithium ions decreases the dynamics of the chains. Additionally, the binding of lithium ions to the sulfonic acids groups was investigated by density functional theory (DFT) calculations. It was found that the local surroundings of the sulfonic acid group have very little effect on the lithium-ion binding energy. Binding energies for a variety of different systems were all calculated to be around 150 kcal/mol. The DFT calculations also show the existence of a structure in which a single lithium ion interacts with two sulfonic acid moieties on different chains. The formation of such "electrostatic cross-links" is believed to be the source of the increased tendency to aggregate and the reduced dynamics in the presence of lithium ions.

Thermochemistry of tantalum-wall cooling system with lithium and sodium working fluids

NASA Technical Reports Server (NTRS)

Tower, L. K.

1972-01-01

Plots are presented which show the distribution of oxygen between liquid lithium and tantalum or niobium, and between liquid sodium and tantalum at elevated temperatures. Additional plots showing the composition of the gas phase above the solutions of oxygen and alkali metal are presented. The use of the plots is illustrated by an example tantalum heat pipe filled with lithium.

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

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.

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

Lithium Polymer Electrolytes and Solid State NMR

NASA Technical Reports Server (NTRS)

Berkeley, Emily R.

2004-01-01

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Measurement of hydrogen solubility and desorption rate in V-4Cr-4Ti and liquid lithium-calcium alloys

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

Park, J.H.; Erck, R.; Park, E.T.

1997-04-01

Hydrogen solubility in V-4Cr-4Ti and liquid lithium-calcium was measured at a hydrogen pressure of 9.09 x 10{sup {minus}4} torr at temperatures between 250 and 700{degrees}C. Hydrogen solubility in V-4Cr-4Ti and liquid lithium decreased with temperature. The measured desorption rate of hydrogen in V-4Cr-4Ti is a thermally activated process; the activation energy is 0.067 eV. Oxygen-charged V-4Cr-4Ti specimens were also investigated to determine the effect of oxygen impurity on hydrogen solubility and desorption in the alloy. Oxygen in V-4Cr-4Ti increases hydrogen solubility and desorption kinetics. To determine the effect of a calcium oxide insulator coating on V-4Cr-4Ti, hydrogen solubility in lithium-calciummore » alloys that contained 0-8.0 percent calcium was also measured. The distribution ratio R of hydrogen between liquid lithium or lithium-calcium and V-4Cr-4Ti increased as temperature decreased (R {approx} 10 and 100 at 700 and 250{degrees}C, respectively). However at <267{degrees}C, solubility data could not be obtained by this method because of the slow kinetics of hydrogen permeation through the vanadium alloy.« less

Self-Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery.

PubMed

Wu, Feng; Chen, Nan; Chen, Renjie; Zhu, Qizhen; Tan, Guoqiang; Li, Li

2016-01-01

The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator-based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable "nanogelator" that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid-like apparent ionic conductivity of 2.93 × 10 -3 S cm -1 at room temperature. The results show that the nanogelator, which possess self-regulating ability, is able to immobilize imidazolium-, pyrrolidinium-, or piperidinium-based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti-nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes.

Material Surface Characteristics and Plasma Performance in the Lithium Tokamak Experiment

NASA Astrophysics Data System (ADS)

Lucia, Matthew James

The performance of a tokamak plasma and the characteristics of the surrounding plasma facing component (PFC) material surfaces strongly influence each other. Despite this relationship, tokamak plasma physics has historically been studied more thoroughly than PFC surface physics. The disparity is particularly evident in lithium PFC research: decades of experiments have examined the effect of lithium PFCs on plasma performance, but the understanding of the lithium surface itself is much less complete. This latter information is critical to identifying the mechanisms by which lithium PFCs affect plasma performance. This research focused on such plasma-surface interactions in the Lithium Tokamak Experiment (LTX), a spherical torus designed to accommodate solid or liquid lithium as the primary PFC. Surface analysis was accomplished via the novel Materials Analysis and Particle Probe (MAPP) diagnostic system. In a series of experiments on LTX, the MAPP x-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS) capabilities were used for in vacuo interrogation of PFC samples. This represented the first application of XPS and TDS for in situ surface analysis of tokamak PFCs. Surface analysis indicated that the thin (dLi ˜ 100nm) evaporative lithium PFC coatings in LTX were converted to Li2O due to oxidizing agents in both the residual vacuum and the PFC substrate. Conversion was rapid and nearly independent of PFC temperature, forming a majority Li2O surface within minutes and an entirely Li2O surface within hours. However, Li2O PFCs were still capable of retaining hydrogen and sequestering impurities until the Li2 O was further oxidized to LiOH, a process that took weeks. For hydrogen retention, Li2O PFCs retained H+ from LTX plasma discharges, but no LiH formation was observed. Instead, results implied that H+ was only weakly-bound, such that it almost completely outgassed as H 2 within minutes. For impurity sequestration, LTX plasma performance---ascertained from plasma current and density measurements---progressively improved as plasma carbon and oxygen impurity levels fell. This was true for PFC conditioning by vacuum baking and argon glow discharge cleaning, as well as by lithium evaporation. Some evidence suggested that impurity sequestration was more important than hydrogen retention in enhancing LTX plasma performance. In contrast with expectations for lithium PFCs, heating the Li2 O PFCs in LTX caused increased plasma impurity levels that tended to reduce plasma performance.

Simulation study of the lithium ion transport mechanism in ternary polymer electrolytes: the critical role of the segmental mobility.

PubMed

Diddens, Diddo; Heuer, Andreas

2014-01-30

We present an extensive molecular dynamics (MD) simulation study of the lithium ion transport in ternary polymer electrolytes consisting of poly(ethylene oxide) (PEO), lithium-bis(trifluoromethane)sulfonimide (LiTFSI), and the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonimide (PYR13TFSI). In particular, we focus on two different strategies by which the ternary electrolytes can be devised, namely by (a) adding the ionic liquid to PEO20LiTFSI and (b) substituting the PEO chains in PEO20LiTFSI by the ionic liquid. To grasp the changes of the overall lithium transport mechanism, we employ an analytical, Rouse-based cation transport model (Maitra et al. Phys. Rev. Lett. 2007, 98, 227802), which has originally been devised for binary PEO-based electrolytes. This model distinguishes three different microscopic transport mechanisms, each quantified by an individual time scale. In the course of our analysis, we extend this mathematical description to account for an entirely new transport mechanism, namely, the TFSI-supported diffusion of lithium ions decoupled from the PEO chains, which emerges for certain stoichiometries. We find that the segmental mobility plays a decisive role in PEO-based polymer electrolytes. That is, whereas the addition of the ionic liquid to PEO20LiTFSI plasticizes the polymer network and thus also increases the lithium diffusion, the amount of free, mobile ether oxygens reduces when substituting the PEO chains by the ionic liquid, which compensates the plasticizing effect. In total, our observations allow us to formulate some general principles about the lithium ion transport mechanism in ternary polymer electrolytes. Moreover, our insights also shed light on recent experimental observations (Joost et al. Electrochim. Acta 2012, 86, 330).

Lithium-ion batteries having conformal solid electrolyte layers

DOEpatents

Kim, Gi-Heon; Jung, Yoon Seok

2014-05-27

Hybrid solid-liquid electrolyte lithium-ion battery devices are disclosed. Certain devices comprise anodes and cathodes conformally coated with an electron insulating and lithium ion conductive solid electrolyte layer.

Lithium-Air and ionic Liquids

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

Kellar, Michael

2015-09-01

The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to themore » typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.« less

A review of lithium and non-lithium based solid state batteries

NASA Astrophysics Data System (ADS)

Kim, Joo Gon; Son, Byungrak; Mukherjee, Santanu; Schuppert, Nicholas; Bates, Alex; Kwon, Osung; Choi, Moon Jong; Chung, Hyun Yeol; Park, Sam

2015-05-01

Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.

Fractionalization beyond Luttinger Liquid in the spectroscopy of Lithium Purple Bronze

NASA Astrophysics Data System (ADS)

Natalia, Lera; Jose, Alvarez

We offer an interpretation for the departures of ARPES and STS spectroscopies experiments in quasi-one-dimensional Lithium Purple Bronze (LiPB) from single-band Luttinger Liquid (LL) theory. We base our calculation on a phenomenological description of the published data proposed in the original experiments and consider two bands crossing the Fermi level. We discuss the breakdown of the LL scaling relation η = α - 1 , the separation of the spinon edge and the holon peak, the phenomenological TL fit to the Energy Distribution Curves (EDC) and the survival of power-like density of states down to 4K. We consider non-critical fluctuations in one of the separated modes in which the electron fractionalize, and discuss under which conditions could be related with the upturn in the resistivity at 20-30K. We discuss the possibility of a gap in such separated mode and its role on the robust one-dimensional behavior. The connection with the proposed triplet superconductivity is at T = 1 . 4 K is also studied. We acknowledge financial support from MINECO FIS2012-37549-C05-03.

Two-cation competition in ionic-liquid-modified electrolytes for lithium ion batteries.

PubMed

Lee, Sang-Young; Yong, Hyun Hang; Lee, Young Joo; Kim, Seok Koo; Ahn, Soonho

2005-07-21

It is a common observation that when ionic liquids are added to electrolytes the performances of lithium ion cells become poor, while the thermal safeties of the electrolytes might be improved. In this study, this behavior is investigated based on the kinetics of ionic diffusion. As a model ionic liquid, we chose butyldimethylimidazolium hexafluorophosphate (BDMIPF(6)). The common solvent was propylene carbonate (PC), and lithium hexafluorophosphate (LiPF(6)) was selected as the lithium conducting salt. Ionic diffusion coefficients are estimated by using a pulsed field gradient NMR technique. From a basic study on the model electrolytes (BDMIPF(6) in PC, LiPF(6) in PC, and BDMIPF(6) + LiPF(6) in PC), it was found that the BDMI(+) from BDMIPF(6) shows larger diffusion coefficients than the Li(+) from LiPF(6). However, the anionic (PF(6)(-)) diffusion coefficients present little difference between the model electrolytes. The higher diffusion coefficient of BDMI(+) than that of Li(+) suggests that the poor C-rate performance of lithium ion cells containing ionic liquids as an electrolyte component can be attributed to the two-cation competition between Li(+) and BDMI(+).

Hybrid electrolytes incorporated with dandelion-like silane-Al2O3 nanoparticles for high-safety high-voltage lithium ion batteries

NASA Astrophysics Data System (ADS)

Xu, Hewei; Shi, Junli; Hu, Guosheng; He, Ying; Xia, Yonggao; Yin, Shanshan; Liu, Zhaoping

2018-07-01

One of the crucial challenge for developing high safety and high voltage lithium ion batteries is to find a reliable electrolyte system. In this work, we report a kind of hybrid electrolytes, which are used for high-voltage lithium ion batteries and are expected to be able to effectively enhance the battery safety. The hybrid electrolytes are obtained by incorporating silane-Al2O3 (Al2O3-ST) into liquid electrolyte, which combines the merits of both solid electrolyte and liquid electrolyte. The Al2O3-ST nanoparticles help to increase lithium-ion transference number and to enhance battery safety, while liquid electrolyte contributes to high ionic conductivity. The cycling stability and rate capacity of LiNi0.5Mn1.5O4/Li batteries are improved by using the hybrid electrolytes. Nail-penetration tests indicate that LiNi0.6Mn0.2Co0.2O2/graphite battery with hybrid electrolyte owns obviously enhanced safety than that using traditional liquid electrolyte. This work provides new insight on electrolyte design for high-safety high-voltage lithium ion batteries.

The use of lithium as a marker for the retention of liquids in the oral cavity after rinsing.

PubMed

Hanning, Sara M; Kieser, Jules A; Ferguson, Martin M; Reid, Malcolm; Medlicott, Natalie J

2014-01-01

The aim of this study was to validate the use of lithium as a marker to indicate the retention of simple liquids in the oral cavity and use this to determine how much liquid is retained in the oral cavity following 30 s of rinsing. This is a validation study in which saliva was spiked with known concentrations of lithium. Twenty healthy participants then rinsed their mouths with either water or a 1 % w/v carboxymethylcellulose (CMC) solution for 30 s before expectorating into a collection cup. Total volume and concentration of lithium in the expectorant were then measured, and the percentage of liquid retained was calculated. The mean amount of liquid retained was 10.4 ± 4.7 % following rinsing with water and 15.3 ± 4.1 % following rinsing with 1 % w/v CMC solution. This difference was significant (p < 0.01). Lithium was useful as a marker for the retention of liquids in the oral cavity, and a value for the amount of water and 1 % w/v CMC solution remaining in the oral cavity following a 30-s rinse was established. The present study quantifies the retention of simple fluids in the oral cavity, validating a technique that may be applied to more complex fluids such as mouth rinses. Further, the application of this method to specific population groups such as those with severe xerostomia may assist in developing effective saliva substitutes.

Designs of LiMIT as a Limiter in the EAST Tokamak

NASA Astrophysics Data System (ADS)

Szott, Matthew; Christenson, Michael; Kalathiparambil, Kishor; Ruzic, David

2016-10-01

Liquid metal plasma facing components (PFCs) provide a constantly refreshing, self-healing surface that can reduce erosion and thermal stress damage to prolong device lifetime, and additionally decrease edge recycling, reduce impurities, and enhance plasma performance. The Liquid Metal Infused Trench (LiMIT) system, developed at UIUC, has demonstrated thermoelectric magnetohydrodynamic (TEMHD) driven flow of liquid lithium through series of solid trenches. This TEMHD effect drives liquid lithium in fusion systems using the plasma heat flux and the toroidal magnetic field, and the surface tension of the liquid lithium maintains a fresh surface on top of the solid trenches. LiMIT has been successfully tested at UIUC as well as HT-7 and Magnum PSI at heat fluxes up to 3 MW/m2. The next step is demonstrating system viability in full-scale fusion-relevant conditions. In collaboration with a team in Hefei, design and testing has begun for a large scale LiMIT system that will act as a limiter in EAST. The designs improve upon previous versions of LiMIT tested at Illinois and incorporate lessons learned from earlier tests of liquid metal PFCs at EAST. Existing infrastructure is used to load and supply lithium to the system, and the LiMIT trenches will help maintain a smooth, fresh surface as well as aid in propelling the lithium out of direct plasma flux to improve heat transfer. Supported by DOE/ALPS DE-FG02-99ER54515.

Lithium insertion in graphite from ternary ionic liquid-lithium salt electrolytes: II. Evaluation of specific capacity and cycling efficiency and stability at room temperature

NASA Astrophysics Data System (ADS)

Lux, Simon F.; Schmuck, Martin; Appetecchi, Giovanni B.; Passerini, Stefano; Winter, Martin; Balducci, Andrea

In this paper we report the results about the use of ternary room temperature ionic liquid-lithium salt mixtures as electrolytes for lithium-ion battery systems. Mixtures of N-methyl- N-propyl pyrrolidinium bis(fluorosulfonyl) imide, PYR 13FSI, and N-butyl- N-methylpyrrolidinium bis(trifluoromethansulfonyl) imide, PYR 14TFSI, with lithium hexafluorophosphate, LiPF 6 and lithium bis(trifluoromethansulfonyl) imide, LiTFSI, containing 5 wt.% of vinylene carbonate (VC) as additive, have been used in combination with a commercial graphite, KS6 TIMCAL. The performance of the graphite electrodes has been considered in term of specific capacity, cycling efficiency and cycling stability. The results clearly show the advantage of the use of ternary mixtures on the performance of the graphite electrode.

A liquid-metal filling system for pumped primary loop space reactors

NASA Astrophysics Data System (ADS)

Crandall, D. L.; Reed, W. C.

Some concepts for the SP-100 space nuclear power reactor use liquid metal as the primary coolant in a pumped loop. Prior to filling ground engineering test articles or reactor systems, the liquid metal must be purified and circulated through the reactor primary system to remove contaminants. If not removed, these contaminants enhance corrosion and reduce reliability. A facility was designed and built to support Department of Energy Liquid Metal Fast Breeder Reactor tests conducted at the Idaho National Engineering Laboratory. This test program used liquid sodium to cool nuclear fuel in in-pile experiments; thus, a system was needed to store and purify sodium inventories and fill the experiment assemblies. This same system, with modifications and potential changeover to lithium or sodium-potassium (NaK), can be used in the Space Nuclear Power Reactor Program. This paper addresses the requirements, description, modifications, operation, and appropriateness of using this liquid-metal system to support the SP-100 space reactor program.

The Role of Dissolved Gas in Ionic Liquid Electrolytes for Secondary Lithium Metal Batteries

DTIC Science & Technology

2013-01-07

devices use lithium-ion batteries comprised of a graphite anode and metal oxide cathode . Lithium, being the third-lightest element, is already synonymous...support shuttling lithium ions (battery cycling) such as the separator, electrolyte, and cathode and anode superstructures contribute most of the...ability of electro-deposit lithium non-dendritically. When lithium is electrodeposited , as during battery charging, it tends to form needle-like

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.

Self‐Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery

PubMed Central

Wu, Feng; Chen, Nan; Zhu, Qizhen; Tan, Guoqiang; Li, Li

2016-01-01

The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator‐based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable “nanogelator” that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid‐like apparent ionic conductivity of 2.93 × 10−3 S cm−1 at room temperature. The results show that the nanogelator, which possess self‐regulating ability, is able to immobilize imidazolium‐, pyrrolidinium‐, or piperidinium‐based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti‐nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes. PMID:27774385

Development of safe, green and high performance ionic liquids-based batteries (ILLIBATT project)

NASA Astrophysics Data System (ADS)

Balducci, A.; Jeong, S. S.; Kim, G. T.; Passerini, S.; Winter, M.; Schmuck, M.; Appetecchi, G. B.; Marcilla, R.; Mecerreyes, D.; Barsukov, V.; Khomenko, V.; Cantero, I.; De Meatza, I.; Holzapfel, M.; Tran, N.

This manuscript presents the work carried out within the European project ILLIBATT, which was dedicated to the development of green, safe and high performance ionic liquids-based lithium batteries. Different types of ionic liquids-based electrolytes were developed in the project, based on different ionic liquids and polymers. Using these electrolytes, the performance of several anodic and cathodic materials has been tested and promising results have been obtained. Also, electrodes were formulated using water soluble binders. Using these innovative components, lithium-ion and lithium-metal battery prototypes (0.7-0.8 Ah) have been assembled and cycled between 100% and 0% SOC. The results of these tests showed that such ionic liquids-based prototypes are able to display high capacity, high coulombic efficiency and high cycle life. Moreover, safety tests showed that the introduction of these alternative electrolytes positively contribute to the safety of the batteries.

Innovative Ionic Liquids: Electrolytes for Ion Power Sources

DTIC Science & Technology

2008-01-01

imide–based ILs can function not only as the electrolyte in a conventional lithium ion battery , but also as a solid nanocomposite separator when...conductivity comparable to the pure ionic liquid. Figure 6 shows the charge-discharge behavior of the micro lithium ion battery created entirely by the

Safe lithium-ion battery with ionic liquid-based electrolyte for hybrid electric vehicles

NASA Astrophysics Data System (ADS)

Damen, Libero; Lazzari, Mariachiara; Mastragostino, Marina

2011-10-01

A lithium-ion battery featuring graphite anode, LiFePO4-C cathode and an innovative, safe, ionic liquid-based electrolyte, was assembled and characterized in terms of specific energy and power after the USABC-DOE protocol for power-assist hybrid electric vehicle (HEV) application. The test results show that the battery surpasses the energy and power goals stated by USABC-DOE and, hence, this safe lithium-ion battery should be suitable for application in the evolving HEV market.

A reversible dendrite-free high-areal-capacity lithium metal electrode

PubMed Central

Wang, Hui; Matsui, Masaki; Kuwata, Hiroko; Sonoki, Hidetoshi; Matsuda, Yasuaki; Shang, Xuefu; Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki

2017-01-01

Reversible dendrite-free low-areal-capacity lithium metal electrodes have recently been revived, because of their pivotal role in developing beyond lithium ion batteries. However, there have been no reports of reversible dendrite-free high-areal-capacity lithium metal electrodes. Here we report on a strategy to realize unprecedented stable cycling of lithium electrodeposition/stripping with a highly desirable areal-capacity (12 mAh cm−2) and exceptional Coulombic efficiency (>99.98%) at high current densities (>5 mA cm−2) and ambient temperature using a diluted solvate ionic liquid. The essence of this strategy, that can drastically improve lithium electrodeposition kinetics by cyclic voltammetry premodulation, lies in the tailoring of the top solid-electrolyte interphase layer in a diluted solvate ionic liquid to facilitate a two-dimensional growth mode. We anticipate that this discovery could pave the way for developing reversible dendrite-free metal anodes for sustainable battery chemistries. PMID:28440299

High energy supercapattery with an ionic liquid solution of LiClO4.

PubMed

Yu, Linpo; Chen, George Z

2016-08-15

A supercapattery combining an ideally polarized capacitor-like electrode and a battery-like electrode is demonstrated theoretically and practically using an ionic liquid electrolyte containing 1-butyl-1-methylpyrrolidinium tri(pentafluoroethyl)trifluorophosphate (BMPyrrFAP), gamma-butyrolactone (γ-GBL) and LiClO4. The electrochemical deposition and dissolution of lithium metal on a platinum and glass carbon electrode were investigated in this ionic liquid solution. The CVs showed that the fresh electrochemically deposited lithium metal was stable in the electrolyte, which encouraged the investigation of this ionic liquid solution in a supercapattery with a lithium battery negative electrode. The active material counted specific energy of the supercapattery based on a lithium negative electrode and an activated carbon (Act-C) positive electrode could reach 230 W h kg(-1) under a galvanostatic charge-discharge current density of 1 mA cm(-2). The positive electrode material (Act-C) was also investigated by CV, AC impedance, SEM and BET. The non-uniform particle size and micropores dominated porous structure of the Act-C enabled its electric double layer capacitor (EDLC) behavior in the ionic liquid solution. The measured specific capacitance of the Act-C in this ionic liquid solution is higher than the same Act-C in aqueous solution, which indicates the Act-C can also perform well in the ionic liquid electrolyte.

NASA Advanced Radiator Technology Development

NASA Astrophysics Data System (ADS)

Koester, J. Kent; Juhasz, Albert J.

1994-07-01

A practical implementation of the two-phase working fluid of lithium and NaK has been developed experimentally for pumped loop radiator designs. The benefits of the high heat capacity and low mass of lithium have been integrated with the shutdown capability enabled by the low freezing temperature of NaK by mixing these liquid metals directly. The stable and reliable start up and shutdown of a lithium/NaK pumped loop has been demonstrated through the development of a novel lithium freeze-separation technique within the flowing header ducts. The results of a highly instrumented liquid metal test loop are presented in which both lithium fraction as well as loop gravitational effects were varied over a wide range of values. Diagnostics based on dual electric probes are presented in which the convective behavior of the lithium component is directly measured during loop operation. The uniform distribution of the lithium after a freeze separation is verified by neutron radiography. The operating regime for reliable freeze/thaw flow behavior is described in terms of correlations based on dimensional analysis.

Space- and time-resolved resistive measurements of liquid metal wall thickness

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

Mirhoseini, S. M. H.; Volpe, F. A., E-mail: fvolpe@columbia.edu

In a fusion reactor internally coated with liquid metal, it will be important to diagnose the thickness of the liquid at various locations in the vessel, as a function of time, and possibly respond to counteract undesired bulging or depletion. The electrical conductance between electrodes immersed in the liquid metal can be used as a simple proxy for the local thickness. Here a matrix of electrodes is shown to provide spatially and temporally resolved measurements of liquid metal thickness in the absence of plasma. First a theory is developed for m × n electrodes, and then it is experimentally demonstratedmore » for 3 × 1 electrodes, as the liquid stands still or is agitated by means of a shaker. The experiments were carried out with Galinstan, but are easily extended to lithium or other liquid metals.« less

Space- and time-resolved resistive measurements of liquid metal wall thickness.

PubMed

Mirhoseini, S M H; Volpe, F A

2016-11-01

In a fusion reactor internally coated with liquid metal, it will be important to diagnose the thickness of the liquid at various locations in the vessel, as a function of time, and possibly respond to counteract undesired bulging or depletion. The electrical conductance between electrodes immersed in the liquid metal can be used as a simple proxy for the local thickness. Here a matrix of electrodes is shown to provide spatially and temporally resolved measurements of liquid metal thickness in the absence of plasma. First a theory is developed for m × n electrodes, and then it is experimentally demonstrated for 3 × 1 electrodes, as the liquid stands still or is agitated by means of a shaker. The experiments were carried out with Galinstan, but are easily extended to lithium or other liquid metals.

A compact self-flowing lithium system for use in an industrial neutron source

NASA Astrophysics Data System (ADS)

Kalathiparambil, Kishor Kumar; Szott, Matthew; Jurczyk, Brian; Ahn, Chisung; Ruzic, David

2016-10-01

A compact trench module to flow liquid lithium in closed loops for handling high heat and particle flux have been fabricated and tested at UIUC. The module was designed to demonstrate the proof of concept in utilizing liquid metals for two principal objectives: i) as self-healing low Z plasma facing components, which is expected to solve the issues facing the current high Z components and ii) using flowing lithium as an MeV-level neutron source. A continuously flowing lithium loop ensures a fresh lithium interface and also accommodate a higher concentration of D, enabling advanced D-Li reactions without using any radioactive tritium. Such a system is expected to have a base yield of 10e7 n/s. For both the applications, the key success factor of the module is attaining the necessary high flow velocity of the lithium especially over the impact area, which will be the disruptive plasma events in fusion reactors and the incident ion beam for the neutron beam source. This was achieved by the efficient shaping of the trenches to exploit the nozzle effect in liquid flow. The compactness of the module, which can also be scaled as desired, was fulfilled by the use of high Tc permanent magnets and air cooled channels attained the necessary temperature gradient for driving the lithium. The design considerations and parameters, experimental arrangements involving lithium filling and attaining flow, data and results obtained will be elaborated. DOE SBIR project DE-SC0013861.

Role of perfluoropolyether-based electrolytes in lithium metal batteries: Implication for suppressed Al current collector corrosion and the stability of Li metal/electrolytes interfaces

NASA Astrophysics Data System (ADS)

Cong, Lina; Liu, Jia; Armand, Michel; Mauger, Alain; Julien, Christian M.; Xie, Haiming; Sun, Liqun

2018-03-01

The development of safe and high performance lithium metal batteries represents a major technological challenge for this new century. Historically, intrinsic instabilities of conventional liquid organic electrolytes induced battery failures and safety issues that hinder the practical utilization of advanced rechargeable lithium metal batteries. Herein, we report a multifunctional perfluoropolyether-based liquid polymer electrolyte (PFPE-MC/LiTFSI), presenting a unique "anion-solvent" interaction. This interaction optimizes the interfacial chemistry of lithium metal batteries, which effectively inhibits the corrosion of aluminum current collectors, suppresses lithium dendrite growth, and also facilitates the formation of a thin and stable SEI layer on Li anode. Even at a high current density of 0.7 mA cm-2, the lithium dendrites do not form after 1360 h of continuous operation. The LiFePO4|PFPE-MC/LiTFSI|Li cell delivers a stable cycling performance with over 99.9% columbic efficiency either at ambient temperature or high temperature, which is significantly superior to those using traditional carbonate electrolytes. In addition, PFPE-MC/LiTFSI electrolyte also possesses eye-catching properties, such as being non-flammable, non-volatile, non-hygroscopic, and existing in the liquid state between -90 °C and 200 °C, which further ensures the high safety of the lithium metal batteries, making this electrolyte promising for the development of high energy lithium metal batteries.

Application of nonflammable electrolyte with room temperature ionic liquids (RTILs) for lithium-ion cells

NASA Astrophysics Data System (ADS)

Nakagawa, Hiroe; Fujino, Yukiko; Kozono, Suguru; Katayama, Yoshihiro; Nukuda, Toshiyuki; Sakaebe, Hikari; Matsumoto, Hajime; Tatsumi, Kuniaki

A mixture of flammable organic solvent and nonflammable room temperature ionic liquid (RTIL) has been investigated as a new concept electrolyte to improve the safety of lithium-ion cells. This study focused on the use of N-methyl- N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13-TFSI) as the RTIL for the flame-retardant additive. It was found that a carbon negative electrode, both graphite and hard carbon, could be used with the mixed electrolyte. A 383562-size lithium-ion trial cell made with the mixed electrolyte showed good discharge capacity, which was equivalent to a cell with conventional organic electrolyte up to a discharge current rate of complete discharge in 1 h. Moreover, the mixed electrolyte was observed to be nonflammable at ionic liquid contents of 40 mass% or more. Thus the mixed electrolyte was found to realize both nonflammability and the good discharge performance of lithium-ion cells with carbon negative electrodes. These results indicate that RTILs have potential as a flame-retardant additive for the organic electrolytes used in lithium-ion cells.

Gettering capsule for removing oxygen from liquid lithium systems

NASA Technical Reports Server (NTRS)

Tower, L. K.; Breitwieser, R.

1973-01-01

Capsule consisting of tantalum shell lined with tantalum screen and partially filled with lithium and pieces of yttrium is immersed in hot lithium stream. Oxygen is removed from stream by being absorbed by gettering capsule. Oxygen passes through capsule wall and into lithium inside capsule where it reacts with yttrium to form Y2O3.

Liquid-metal-fed Pulsed Plasma Thrusters for In-space Propulsion

NASA Technical Reports Server (NTRS)

Markusic, Thomas E.

2004-01-01

Liquid metal propellants may provide a path toward more reliable and efficient pulsed plasma thrusters (PPTs). Conceptual thruster designs which eliminate the need for high current switches and propellant metering valves are described. Propellant loading techniques are suggested that show promise to increase thruster propellant utilization, dynamic, and electrical efficiency. Calibration results from a compact, electromagnetically-pumped propellant feed system are presented. Results for lithium and gallium propellants show capability to meter propellant at flow rates up to 10 +/- 0.1 mg/s. Experiments investigating the initiation of arc discharges using liquid metal droplets are presented. High speed photography and laser interferometry provide spatially and temporally resolved information on the decomposition of liquid metal droplets , and the evolution of the accelerating current channel.

The conversion of a room temperature NaK loop to a high temperature MHD facility for Li/V blanket testing

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

Reed, C.B.; Haglund, R.C.; Miller, M.E.

1996-12-31

The Vanadium/Lithium system has been the recent focus of ANL`s Blanket Technology Pro-ram, and for the last several years, ANL`s Liquid Metal Blanket activities have been carried out in direct support of the ITER (International Thermonuclear Experimental Reactor) breeding blanket task area. A key feasibility issue for the ITER Vanadium/Lithium breeding blanket is the Near the development of insulator coatings. Design calculations, Hua and Gohar, show that an electrically insulating layer is necessary to maintain an acceptably low magneto-hydrodynamic (MHD) pressure drop in the current ITER design. Consequently, the decision was made to convert Argonne`s Liquid Metal EXperiment (ALEX) frommore » a 200{degrees}C NaK facility to a 350{degrees}C lithium facility. The upgraded facility was designed to produce MHD pressure drop data, test section voltage distributions, and heat transfer data for mid-scale test sections and blanket mockups at Hartmann numbers (M) and interaction parameters (N) in the range of 10{sup 3} to 10{sup 5} in lithium at 350{degrees}C. Following completion of the upgrade work, a short performance test was conducted, followed by two longer multiple-hour, MHD tests, all at 230{degrees}C. The modified ALEX facility performed up to expectations in the testing. MHD pressure drop and test section voltage distributions were collected at Hartmann numbers of 1000.« less

Conversion of a room temperature NaK loop to a high temperature MHD facility for Li/V blanket testing

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

Reed, C.B.; Haglund, R.C.; Miller, M.E.

1996-12-31

The Vanadium/Lithium system has been the recent focus of ANL`s Blanket Technology Program, and for the last several years, ANL`s Liquid Metal Blanket activities have been carried out in direct support of the ITER (International Thermonuclear Experimental Reactor) breeding blanket task area. A key feasibility issue for the ITER Vanadium/Lithium breeding blanket is the development of insulator coatings. Design calculations, Hua and Gohar, show that an electrically insulating layer is necessary to maintain an acceptably low magnetohydrodynamic (MHD) pressure drop in the current ITER design. Consequently, the decision was made to convert Argonne`s Liquid Metal EXperiment (ALEX) from a 200{degree}Cmore » NaK facility to a 350{degree}C lithium facility. The upgraded facility was designed to produce MHD pressure drop data, test section voltage distributions, and heat transfer data for mid-scale test sections and blanket mockups at Hartmann numbers (M) and interaction parameters (N) in the range of 10{sup 3} to 10{sup 5} in lithium at 350{degree}C. Following completion of the upgrade work, a short performance test was conducted, followed by two longer, multiple-hour, MHD tests, all at 230{degree}C. The modified ALEX facility performed up to expectations in the testing. MHD pressure drop and test section voltage distributions were collected at Hartmann numbers of 1000. 4 refs., 2 figs.« less

Modeling of surface temperature effects on mixed material migration in NSTX-U

NASA Astrophysics Data System (ADS)

Nichols, J. H.; Jaworski, M. A.; Schmid, K.

2016-10-01

NSTX-U will initially operate with graphite walls, periodically coated with thin lithium films to improve plasma performance. However, the spatial and temporal evolution of these films during and after plasma exposure is poorly understood. The WallDYN global mixed-material surface evolution model has recently been applied to the NSTX-U geometry to simulate the evolution of poloidally inhomogenous mixed C/Li/O plasma-facing surfaces. The WallDYN model couples local erosion and deposition processes with plasma impurity transport in a non-iterative, self-consistent manner that maintains overall material balance. Temperature-dependent sputtering of lithium has been added to WallDYN, utilizing an adatom sputtering model developed from test stand experimental data. Additionally, a simplified temperature-dependent diffusion model has been added to WallDYN so as to capture the intercalation of lithium into a graphite bulk matrix. The sensitivity of global lithium migration patterns to changes in surface temperature magnitude and distribution will be examined. The effect of intra-discharge increases in surface temperature due to plasma heating, such as those observed during NSTX Liquid Lithium Divertor experiments, will also be examined. Work supported by US DOE contract DE-AC02-09CH11466.

RAPID-L Highly Automated Fast Reactor Concept Without Any Control Rods (2) Critical experiment of lithium-6 used in LEM and LIM

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

Tsunoda, Hirokazu; Sato, Osamu; Okajima, Shigeaki

2002-07-01

In order to achieve fully automated reactor operation of RAPID-L reactor, innovative reactivity control systems LEM, LIM, and LRM are equipped with lithium-6 as a liquid poison. Because lithium-6 has not been used as a neutron absorbing material of conventional fast reactors, measurements of the reactivity worth of Lithium-6 were performed at the Fast Critical Assembly (FCA) of Japan Atomic Energy Research Institute (JAERI). The FCA core was composed of highly enriched uranium and stainless steel samples so as to simulate the core spectrum of RAPID-L. The samples of 95% enriched lithium-6 were inserted into the core parallel to themore » core axis for the measurement of the reactivity worth at each position. It was found that the measured reactivity worth in the core region well agreed with calculated value by the method for the core designs of RAPID-L. Bias factors for the core design method were obtained by comparing between experimental and calculated results. The factors were used to determine the number of LEM and LIM equipped in the core to achieve fully automated operation of RAPID-L. (authors)« less

Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

PubMed Central

Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

2016-01-01

Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

Kamlet-Taft solvent parameters, NMR spectroscopic analysis and thermoelectrochemistry of lithium-glyme solvate ionic liquids and their dilute solutions.

PubMed

Black, Jeffrey J; Dolan, Andrew; Harper, Jason B; Aldous, Leigh

2018-06-06

Solvate ionic liquids are a relatively new class of liquids produced by combining a coordinating solvent with a salt. They have a variety of uses and their suitability for such depends upon the ratio of salt to coordinating solvent. This work investigates the Kamlet-Taft solvent parameters of, NMR chemical shifts of nuclei in, and thermoelectrochemistry of a selected set of solvate ionic liquids produced from glymes (methyl terminated oligomers of ethylene glycol) and lithium bis(trifluoromethylsulfonyl)imide at two different compositions. The aim is to improve the understanding of the interactions occurring in these ionic liquids to help select suitable solvate ionic liquids for future applications.

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Tigelaar, Dean M.; Chapin, Kara; Bennett, William R.

2007-01-01

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Decomposition of Imidazolium-Based Ionic Liquids in Contact with Lithium Metal.

PubMed

Schmitz, Paulo; Jakelski, Rene; Pyschik, Marcelina; Jalkanen, Kirsi; Nowak, Sascha; Winter, Martin; Bieker, Peter

2017-03-09

Ionic liquids (ILs) are considered to be suitable electrolyte components for lithium-metal batteries. Imidazolium cation based ILs were previously found to be applicable for battery systems with a lithium-metal negative electrode. However, herein it is shown that, in contrast to the well-known IL N-butyl-N-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide ([Pyr 14 ][TFSI]), 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C2MIm][TFSI]) and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C4MIm][TFSI]) are chemically unstable versus metallic lithium. A lithium-metal sheet was immersed in pure imidazolium-based IL samples and aged at 60 °C for 28 days. Afterwards, the aged IL samples were investigated to deduce possible decomposition products of the imidazolium cation. The chemical instability of the ILs in contact with lithium metal and a possible decomposition starting point are shown for the first time. Furthermore, the investigated imidazolium-based ILs can be utilized for lithium-metal batteries through the addition of the solid-electrolyte interphase (SEI) film-forming additive fluoroethylene carbonate. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolyte compositions for lithium ion batteries

DOEpatents

Sun, Xiao-Guang; Dai, Sheng; Liao, Chen

2016-03-29

The invention is directed in a first aspect to an ionic liquid of the general formula Y.sup.+Z.sup.-, wherein Y.sup.+ is a positively-charged component of the ionic liquid and Z.sup.- is a negatively-charged component of the ionic liquid, wherein Z.sup.- is a boron-containing anion of the following formula: ##STR00001## The invention is also directed to electrolyte compositions in which the boron-containing ionic liquid Y.sup.+Z.sup.- is incorporated into a lithium ion battery electrolyte, with or without admixture with another ionic liquid Y.sup.+X.sup.- and/or non-ionic solvent and/or non-ionic solvent additive.

Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles

DOE PAGES

He, Qing; Williams, Neil J.; Oh, Ju; ...

2018-05-25

LiCl is a classic "hard" ion salt that is present in lithium-rich brines and a key component in end-of-life materials (i.e., used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Here in this paper, we describe two ditopic calix[4]pyrrole-based ion pair receptors (2 and 3), that are capable of selectively capturing LiCl. Under solid-liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl-KCl salt mixture containing as little as 1% LiCl with ~100% selectivity, while receptor 3 achieved similar separations when the LiCl levelmore » was as low as 200 ppm. Under liquid-liquid extraction conditions using nitrobenzene as the non-aqueous phase, the extraction preference displayed by 2 is KCl > NaCl > LiCl. Lastly, in contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.« less

Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles

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

He, Qing; Williams, Neil J.; Oh, Ju

LiCl is a classic "hard" ion salt that is present in lithium-rich brines and a key component in end-of-life materials (i.e., used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Here in this paper, we describe two ditopic calix[4]pyrrole-based ion pair receptors (2 and 3), that are capable of selectively capturing LiCl. Under solid-liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl-KCl salt mixture containing as little as 1% LiCl with ~100% selectivity, while receptor 3 achieved similar separations when the LiCl levelmore » was as low as 200 ppm. Under liquid-liquid extraction conditions using nitrobenzene as the non-aqueous phase, the extraction preference displayed by 2 is KCl > NaCl > LiCl. Lastly, in contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.« less

Preparation and electrochemical characterization of ionic-conducting lithium lanthanum titanate oxide/polyacrylonitrile submicron composite fiber-based lithium-ion battery separators

NASA Astrophysics Data System (ADS)

Liang, Yinzheng; Ji, Liwen; Guo, Bingkun; Lin, Zhan; Yao, Yingfang; Li, Ying; Alcoutlabi, Mataz; Qiu, Yiping; Zhang, Xiangwu

Lithium lanthanum titanate oxide (LLTO)/polyacrylonitrile (PAN) submicron composite fiber-based membranes were prepared by electrospinning dispersions of LLTO ceramic particles in PAN solutions. These ionic-conducting LLTO/PAN composite fiber-based membranes can be directly used as lithium-ion battery separators due to their unique porous structure. Ionic conductivities were evaluated after soaking the electrospun LLTO/PAN composite fiber-based membranes in a liquid electrolyte, 1 M lithium hexafluorophosphate (LiPF 6) in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (1:1 vol). It was found that, among membranes with various LLTO contents, 15 wt.% LLTO/PAN composite fiber-based membranes provided the highest ionic conductivity, 1.95 × 10 -3 S cm -1. Compared with pure PAN fiber membranes, LLTO/PAN composite fiber-based membranes had greater liquid electrolyte uptake, higher electrochemical stability window, and lower interfacial resistance with lithium. In addition, lithium//1 M LiPF 6/EC/EMC//lithium iron phosphate cells containing LLTO/PAN composite fiber-based membranes as the separator exhibited high discharge specific capacity of 162 mAh g -1 and good cycling performance at 0.2 C rate at room temperature.

Parabolic lithium mirror for a laser-driven hot plasma producing device

DOEpatents

Baird, James K.

1979-06-19

A hot plasma producing device is provided, wherein pellets, singly injected, of frozen fuel are each ignited with a plurality of pulsed laser beams. Ignition takes place within a void area in liquid lithium contained within a pressure vessel. The void in the liquid lithium is created by rotating the pressure vessel such that the free liquid surface of molten lithium therein forms a paraboloid of revolution. The paraboloid functions as a laser mirror with a reflectivity greater than 90%. A hot plasma is produced when each of the frozen deuterium-tritium pellets sequentially arrive at the paraboloid focus, at which time each pellet is illuminated by the plurality of pulsed lasers whose rays pass through circular annuli across the top of the paraboloid. The beams from the lasers are respectively directed by associated mirrors, or by means of a single conical mirror in another embodiment, and by the mirror-like paraboloid formed by the rotating liquid lithium onto the fuel pellet such that the optical flux reaching the pellet can be made to be uniform over 96% of the pellet surface area. The very hot plasma produced by the action of the lasers on the respective singly injected fuel pellets in turn produces a copious quantity of neutrons and X-rays such that the device has utility as a neutron source or as an x-ray source. In addition, the neutrons produced in the device may be utilized to produce tritium in a lithium blanket and is thus a mechanism for producing tritium.

Solid-Liquid Electrolyte as a Nanoion Modulator for Dendrite-Free Lithium Anodes.

PubMed

Wen, Kaihua; Wang, Yanlei; Chen, Shimou; Wang, Xi; Zhang, Suojiang; Archer, Lynden A

2018-06-20

Rechargeable lithium (Li) metal batteries are considered the most promising of Li-based energy storage technologies. However, tree-like dendrite produced by irregular Li + electrodeposition restricts it wide applications. Herein, based on a cation-microphase-regulation strategy, we create solid-liquid electrolytes (SLEs) by absorbing commercial liquid electrolytes into polyethylene glycol (PEG) engineered nanoporous Al 2 O 3 ceramic membranes. By means of molecular dynamics simulations and comprehensive experiments, we show that Li ions are regulated and promoted in the two microphases, the channel phase and nonchannel phase, respectively. The channel phase can achieve homogeneous Li + flux distribution by multiple mechanisms, including its uniform array of nanochannels and ability to suppress lateral dendrite growth by its high modulus. In the nonchannel phase, PEG chains swollen by electrolyte facilitate desolvation and fast conduction of Li + . As a result, the studied SLEs exhibit high ionic conductivity, low interfacial resistance, and the unique ability to stabilize deposition at the Li anode. By means of galvanostatic cycling studies in symmetric Li cells and Li/Li 4 Ti 5 O 12 cells, we further show that the materials open a path to Li metal batteries with excellent cycling performance.

Experiments with lithium limiter on T-11M tokamak and applications of the lithium capillary-pore system in future fusion reactor devices

NASA Astrophysics Data System (ADS)

Mirnov, S. V.; Azizov, E. A.; Evtikhin, V. A.; Lazarev, V. B.; Lyublinski, I. E.; Vertkov, A. V.; Prokhorov, D. Yu

2006-06-01

The paper is an overview of recent results of Li limiter testing in T-11M tokamak. The lithium limiter is based on the capillary-pore system (CPS) concept. The Li erosion process and deuterium (D2) and helium (He) sorption by Li first wall were investigated. The ability of capillary forces to confine the liquid Li in the CPS limiter during disruption was demonstrated. The idea of combined lithium limiter with thin (0.6 mm) CPS coating as a solution of the heat removal problem was realized. As a result the quasi steady-state tokamak regime with duration up to 0.3 s and clean (Zeff = 1) deuterium plasma has been achieved. The temporal evolution of the lithium surface temperature during discharge was measured by a IR radiometer and then was recalculated to the surface power load. For the estimation of the Li limiter erosion the Li neutral and ions spectral line emission were observed. The increase in lithium erosion as a result of limiter heating was discovered. The radial distribution of plasma column radiation measurements showed up to 90% of the total radiation losses in a relatively thin (5 cm) boundary layer and only 10% in a plasma centre during discharges with high Li influx. Oscillations of Li emission and saw-tooth-like oscillations of the limiter surface temperature have been detected in discharge regimes with highest Li limiter temperature (>600 °C). A version of Li CPS first wall of DEMO reactor and Li CPS limiter experiment in the International Thermonuclear Energy Reactor are suggested.

Shrinkage void formation and its effect on freeze and thaw processes of lithium and lithium-fluoride for space applications

NASA Astrophysics Data System (ADS)

Yang, Jae-Young; El-Genk, M. S.

1991-07-01

The effects of shrinkage void forming during freezing of lithium and lithium-fluoride on subsequent thaw processes are investigated using a numerical scheme that is based on a single (solid/liquid) cell approach. Results show that a void forming at the wall appreciably reduces the solid-liquid interface velocity, during both freeze and thaw, and causes a substantial rise in the wall temperature during thaw. However, in the case of Li, the maximum wall temperature was much lower than the melting temperature of PWC-11, which is used as the structure material in the SP-100 system. Hence, it is concluded that a formation of hot spots is unlikely during the startup or restart of the SP-100 system.

Shrinkage void formation and its effect on freeze and thaw processes of lithium and lithium-fluoride for space applications

NASA Technical Reports Server (NTRS)

Yang, Jae Y.; El-Genk, Mohamed S.

1991-01-01

The effects of shrinkage void forming during freezing of lithium and lithium fluoride on subsequent thaw processes are investigated using a numerical scheme that is based on a single (solid/liquid) cell approach. Results show that a void forming at the wall appreciably reduces the solid-liquid interface velocity, during both freeze and thaw, and causes a substantial rise in the wall temperature during thaw. However, in the case of Li, the maximum wall temperature was much lower than the melting temperature of PWC-11, which is used as the structure material in the SP-100 system. Hence, it is concluded that a formation of hot spots is unlikely during the startup or restart of the SP-100 system.

Survey of Commercial Small Lithium Polymer Batteries

DTIC Science & Technology

2007-09-19

by a liquid electrolyte which is made conductive for Li ions by the addition of a salt such as lithium hexafluorophosphate (LiPF6). The...Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6110--07-9073 Survey of Commercial Small Lithium Polymer Batteries September 19, 2007... Lithium Polymer Batteries Arnold M. Stux and Karen Swider-Lyons Naval Research Laboratory 4555 Overlook Avenue, SW Washington, DC 20375-5320 NRL/MR

Recycling positive-electrode material of a lithium-ion battery

DOEpatents

Sloop, Steven E.

2017-11-21

Examples are disclosed of methods to recycle positive-electrode material of a lithium-ion battery. In one example, the positive-electrode material is heated under pressure in a concentrated lithium hydroxide solution. After heating, the positive-electrode material is separated from the concentrated lithium hydroxide solution. After separating, the positive electrode material is rinsed in a basic liquid. After rinsing, the positive-electrode material is dried and sintered.

Material Surface Characteristics and Plasma Performance in the Lithium Tokamak Experiment

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

Lucia, Matthew James

The performance of a tokamak plasma and the characteristics of the surrounding plasma facing component (PFC) material surfaces strongly influence each other. Despite this relationship, tokamak plasma physics has historically been studied more thoroughly than PFC surface physics. The disparity is particularly evident in lithium PFC research: decades of experiments have examined the effect of lithium PFCs on plasma performance, but the understanding of the lithium surface itself is much less complete. This latter information is critical to identifying the mechanisms by which lithium PFCs affect plasma performance. This research focused on such plasma-surface interactions in the Lithium Tokamak Experimentmore » (LTX), a spherical torus designed to accommodate solid or liquid lithium as the primary PFC. Surface analysis was accomplished via the novel Materials Analysis and Particle Probe (MAPP) diagnostic system. In a series of experiments on LTX, the MAPP x-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS) capabilities were used for in vacuo interrogation of PFC samples. This represented the first application of XPS and TDS for in situ surface analysis of tokamak PFCs. Surface analysis indicated that the thin (d ~ 100nm) evaporative lithium PFC coatings in LTX were converted to Li2O due to oxidizing agents in both the residual vacuum and the PFC substrate. Conversion was rapid and nearly independent of PFC temperature, forming a majority Li2O surface within minutes and an entirely Li2O surface within hours. However, Li2O PFCs were still capable of retaining hydrogen and sequestering impurities until the Li2O was further oxidized to LiOH, a process that took weeks. For hydrogen retention, Li2O PFCs retained H+ from LTX plasma discharges, but no LiH formation was observed. Instead, results implied that H+ was only weakly-bound, such that it almost completely outgassed as H2 within minutes. For impurity sequestration, LTX plasma performance—ascertained from plasma current and density measurements—progressively improved as plasma carbon and oxygen impurity levels fell. This was true for PFC conditioning by vacuum baking and argon glow discharge cleaning, as well as by lithium evaporation. Some evidence suggested that impurity sequestration was more important than hydrogen retention in enhancing LTX plasma performance. In contrast with expectations for lithium PFCs, heating the Li2O PFCs in LTX caused increased plasma impurity levels that tended to reduce plasma performance.« less

Dendrite-Suppressed Lithium Plating from a Liquid Electrolyte via Wetting of Li 3N

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

Park, Kyusung; Goodenough, John B.

Lithium metal is an ultimate anode material to provide the highest energy density for a given cathode by providing a higher capacity and cell voltage. However, lithium is not used as the anode in commercial lithium-ion batteries because electrochemical dendrite formation and growth during charge can induce a cell short circuit that ignites the flammable liquid electrolyte. Plating of lithium through a bed of Li 3N particles is shown to transform dendrite growth into a 3D lithium network formed by wetting the particle surfaces; plating through a Li 3N particle is without dendrite nucleation. The Li 3N particles create amore » higher overpotential during Li deposition than that with dendrite growth in galvanostatic charge/discharge tests. The characteristic overpotential increase is correlated with the morphological changes and a more isotropic growth behavior. The Li 3N-modified Li electrode shows a stable cycling performance at 0.5 and 1.0 mA cm -2 for more than 100 cycles. In this paper, the origin of the bonding responsible for wetting of the Li 3N particles by lithium and for plating through a Li 3N particle is discussed.« less

Dendrite-Suppressed Lithium Plating from a Liquid Electrolyte via Wetting of Li 3N

DOE PAGES

Park, Kyusung; Goodenough, John B.

2017-07-10

Lithium metal is an ultimate anode material to provide the highest energy density for a given cathode by providing a higher capacity and cell voltage. However, lithium is not used as the anode in commercial lithium-ion batteries because electrochemical dendrite formation and growth during charge can induce a cell short circuit that ignites the flammable liquid electrolyte. Plating of lithium through a bed of Li 3N particles is shown to transform dendrite growth into a 3D lithium network formed by wetting the particle surfaces; plating through a Li 3N particle is without dendrite nucleation. The Li 3N particles create amore » higher overpotential during Li deposition than that with dendrite growth in galvanostatic charge/discharge tests. The characteristic overpotential increase is correlated with the morphological changes and a more isotropic growth behavior. The Li 3N-modified Li electrode shows a stable cycling performance at 0.5 and 1.0 mA cm -2 for more than 100 cycles. In this paper, the origin of the bonding responsible for wetting of the Li 3N particles by lithium and for plating through a Li 3N particle is discussed.« less

A Comparison of the Predictive Capabilities of the Embedded-Atom Method and Modified Embedded-Atom Method Potentials for Lithium

DOE PAGES

Vella, Joseph R.; Stillinger, Frank H.; Panagiotopoulos, Athanassios Z.; ...

2015-07-23

Here, we compare six lithium potentials by examining their ability to predict coexistence properties and liquid structure using molecular dynamics. All potentials are of the embedded-atom-method (EAM) type. The coexistence properties we focus on are the melting curve, vapor pressure, saturated liquid density, and vapor-liquid surface tension. For each property studied, the simulation results are compared to available experimental data in order to properly assess the accuracy of each potential. We find that the Cui 2NN MEAM is the most robust potential, giving adequate agreement with most of the properties examined. For example, the zero-pressure melting point of this potentialmore » is shown to be around 443 K, while experimentally is it about 454 K. This potential also gives excellent agreement with saturated liquid densities, even though no liquid properties were used in the fitting procedure. Our study allows us to conclude that the Cui 2NN MEAM should be used for further simulations of lithiums.« less

Lithium-based surfaces controlling fusion plasma behavior at the plasma-material interfacea)

NASA Astrophysics Data System (ADS)

Allain, Jean Paul; Taylor, Chase N.

2012-05-01

The plasma-material interface and its impact on the performance of magnetically confined thermonuclear fusion plasmas are considered to be one of the key scientific gaps in the realization of nuclear fusion power. At this interface, high particle and heat flux from the fusion plasma can limit the material's lifetime and reliability and therefore hinder operation of the fusion device. Lithium-based surfaces are now being used in major magnetic confinement fusion devices and have observed profound effects on plasma performance including enhanced confinement, suppression and control of edge localized modes (ELM), lower hydrogen recycling and impurity suppression. The critical spatial scale length of deuterium and helium particle interactions in lithium ranges between 5-100 nm depending on the incident particle energies at the edge and magnetic configuration. Lithium-based surfaces also range from liquid state to solid lithium coatings on a variety of substrates (e.g., graphite, stainless steel, refractory metal W/Mo/etc., or porous metal structures). Temperature-dependent effects from lithium-based surfaces as plasma facing components (PFC) include magnetohydrodynamic (MHD) instability issues related to liquid lithium, surface impurity, and deuterium retention issues, and anomalous physical sputtering increase at temperatures above lithium's melting point. The paper discusses the viability of lithium-based surfaces in future burning-plasma environments such as those found in ITER and DEMO-like fusion reactor devices.

Liquid-free rechargeable Li polymer battery

NASA Astrophysics Data System (ADS)

Matsui, S.; Muranaga, T.; Higobashi, H.; Inoue, S.; Sakai, T.

Safety is a key concern for high-power energy storage systems such as will be required for electric vehicles. Present lithium ion batteries, which use a flammable organic liquid electrolyte, lack inherent safety. Our approach in solving this problem is to replace the liquid electrolyte with a liquid-free polymer electrolyte. Data of the composition of the positive electrode, charge-discharge and cycle-life capability are presented. The cell using metallic lithium anode and crosslinked polymer electrolyte P(EO/MEEGE/AGE)-LiTFSI showed a discharge capacity of 134 mAh g -1 of LiCoO 2 at 60°C and 140 mAh g -1 at 140°C.

Compositional depth profiles of the type 316 stainless steel undergone the corrosion in liquid lithium using laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Li, Ying; Ke, Chuan; Liu, Xiang; Gou, Fujun; Duan, Xuru; Zhao, Yong

2017-12-01

Liquid metal lithium cause severe corrosion on the surface of metal structure material that used in the blanket and first wall of fusion device. Fast and accurate compositional depth profile measurement for the boundary layer of the corroded specimen will reveal the clues for the understanding and evaluation of the liquid lithium corrosion process as well as the involved corrosion mechanism. In this work, the feasibility of laser-induced breakdown spectroscopy for the compositional depth profile analysis of type 316 stainless steel which was corroded by liquid lithium in certain conditions was demonstrated. High sensitivity of LIBS was revealed especially for the corrosion medium Li in addition to the matrix elements of Fe, Cr, Ni and Mn by the spectral analysis of the plasma emission. Compositional depth profile analysis for the concerned elements which related to corrosion was carried out on the surface of the corroded specimen. Based on the verified local thermodynamic equilibrium shot-by-shot along the depth profile, the matrix effect was evaluated as negligible by the extracted physical parameter of the plasmas generated by each laser pulse in the longitudinal depth profile. In addition, the emission line intensity ratios were introduced to further reduce the impact on the emission line intensity variations arise from the strong inhomogeneities on the corroded surface. Compositional depth profiles for the matrix elements of Fe, Cr, Ni, Mn and the corrosion medium Li were constructed with their measured relative emission line intensities. The distribution and correlations of the concerned elements in depth profile may indicate the clues to the complicated process of composition diffusion and mass transfer. The results obtained demonstrate the potentiality of LIBS as an effective technique to perform spectrochemical measurement in the research fields of liquid metal lithium corrosion.

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.

Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Tigelaar, Dean M.

2009-01-01

Polyimide-PEO copolymers (PEO signifies polyethylene oxide) that have branched rod-coil molecular structures and that can be cured into film form at room temperature have been invented for use as gel electrolytes for lithium-ion electric-power cells. These copolymers offer an alternative to previously patented branched rod-coil polyimides that have been considered for use as polymer electrolytes and that must be cured at a temperature of 200 C. In order to obtain sufficient conductivity for lithium ions in practical applications at and below room temperature, it is necessary to imbibe such a polymer with a suitable carbonate solvent or ionic liquid, but the high-temperature cure makes it impossible to incorporate and retain such a liquid within the polymer molecular framework. By eliminating the high-temperature cure, the present invention makes it possible to incorporate the required liquid.

Electrochemical characterisation of a lithium-ion battery electrolyte based on mixtures of carbonates with a ferrocene-functionalised imidazolium electroactive ionic liquid.

PubMed

Forgie, John C; El Khakani, Soumia; MacNeil, Dean D; Rochefort, Dominic

2013-05-28

Electrolytic solutions of lithium-ion batteries can be modified with additives to improve their stability and safety. Electroactive molecules can be used as such additives to act as an electron (redox) shuttle between the two electrodes to prevent overcharging. The electroactive ionic liquid, 1-ferrocenylmethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (TFSI), was synthesised and its electrochemical properties were investigated when diluted with ethylene carbonate-diethyl carbonate solvent at various concentrations. Cyclic voltammetry data were gathered to determine the redox potential, diffusion coefficient and heterogeneous rate constants of the electroactive imidazolium TFSI ionic liquid in the carbonate solution. The properties of this molecule as an additive in lithium battery electrolytes were studied in standard coin cells with a metallic Li anode and a Li4Ti5O12 cathode.

Dissociation of doubly charged clusters of lithium acetate: Asymmetric fission and breakdown of the liquid drop model: Dissociation of doubly charged clusters of lithium acetate

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

Shukla, Anil

2016-06-08

Unimolecular and collision-induced dissociation of doubly charged lithium acetate clusters, (CH3COOLi)nLi22+, demonstrated that Coulomb fission via charge separation is the dominant dissociation process with no contribution from the neutral evaporation processes for all such ions from the critical limit to larger cluster ions, although latter process have normally been observed in all earlier studies. These results are clearly in disagreement with the Rayleigh’s liquid drop model that has been used successfully to predict the critical size and explain the fragmentation behavior of multiply charged clusters.

Production of heavy water

DOEpatents

Spencer, Larry S.; Brown, Sam W.; Phillips, Michael R.

2017-06-06

Disclosed are methods and apparatuses for producing heavy water. In one embodiment, a catalyst is treated with high purity air or a mixture of gaseous nitrogen and oxygen with gaseous deuterium all together flowing over the catalyst to produce the heavy water. In an alternate embodiment, the deuterium is combusted to form the heavy water. In an alternate embodiment, gaseous deuterium and gaseous oxygen is flowed into a fuel cell to produce the heavy water. In various embodiments, the deuterium may be produced by a thermal decomposition and distillation process that involves heating solid lithium deuteride to form liquid lithium deuteride and then extracting the gaseous deuterium from the liquid lithium deuteride.

Synergistic Effects of Mixing Sulfone and Ionic Liquid as Safe Electrolytes for Lithium Sulfur Batteries

DOE PAGES

Liao, Chen; Guo, Bingkun; Sun, Xiao-Guang; ...

2014-11-26

A strategy of mixing both an ionic liquid and sulfone is reported to give synergistic effects of reducing viscosity, increasing ionic conductivity, reducing polysulfide dissolution, and improving safety. The mixtures of ionic liquids and sulfones also show distinctly different physicochemical properties, including thermal properties and crystallization behavior. By using these electrolytes, lithium sulfur batteries assembled with lithium and mesoporous carbon composites show a reversible specific capacity of 1265 mAhg- 1 (second cycle) by using 40% 1.0 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in N-methyl-Npropylpyrrolidinium bis(trifluoromethylsulfonyl)imide with 60% 1.0 M LiTFSI in methylisopropylsulfone in the first cycle. This capacity is slightly lower thanmore » that obtained in pure 1.0 M LiTFSI as the sulfone electrolyte; however, it exhibits excellent cycling stability and remains as high as 655 mAhg 1 even after 50 cycles. This strategy provides a method to alleviate polysulfide dissolution and redox shuttle phenomena, at the same time, with improved ionic conductivity.« less

Current status of environmental, health, and safety issues of lithium ion electric vehicle batteries

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

Vimmerstedt, L.J.; Ring, S.; Hammel, C.J.

The lithium ion system considered in this report uses lithium intercalation compounds as both positive and negative electrodes and has an organic liquid electrolyte. Oxides of nickel, cobalt, and manganese are used in the positive electrode, and carbon is used in the negative electrode. This report presents health and safety issues, environmental issues, and shipping requirements for lithium ion electric vehicle (EV) batteries. A lithium-based electrochemical system can, in theory, achieve higher energy density than systems using other elements. The lithium ion system is less reactive and more reliable than present lithium metal systems and has possible performance advantages overmore » some lithium solid polymer electrolyte batteries. However, the possibility of electrolyte spills could be a disadvantage of a liquid electrolyte system compared to a solid electrolyte. The lithium ion system is a developing technology, so there is some uncertainty regarding which materials will be used in an EV-sized battery. This report reviews the materials presented in the open literature within the context of health and safety issues, considering intrinsic material hazards, mitigation of material hazards, and safety testing. Some possible lithium ion battery materials are toxic, carcinogenic, or could undergo chemical reactions that produce hazardous heat or gases. Toxic materials include lithium compounds, nickel compounds, arsenic compounds, and dimethoxyethane. Carcinogenic materials include nickel compounds, arsenic compounds, and (possibly) cobalt compounds, copper, and polypropylene. Lithiated negative electrode materials could be reactive. However, because information about the exact compounds that will be used in future batteries is proprietary, ongoing research will determine which specific hazards will apply.« less

Developing High-Performance Lithium Metal Anode in Liquid Electrolytes: Challenges and Progress.

PubMed

Li, Sa; Jiang, Mengwen; Xie, Yong; Xu, Hui; Jia, Junyao; Li, Ju

2018-04-01

Lithium metal anodes are potentially key for next-generation energy-dense batteries because of the extremely high capacity and the ultralow redox potential. However, notorious safety concerns of Li metal in liquid electrolytes have significantly retarded its commercialization: on one hand, lithium metal morphological instabilities (LMI) can cause cell shorting and even explosion; on the other hand, breaking of the grown Li arms induces the so-called "dead Li"; furthermore, the continuous consumption of the liquid electrolyte and cycleable lithium also shortens cell life. The research community has been seeking new strategies to protect Li metal anodes and significant progress has been made in the last decade. Here, an overview of the fundamental understandings of solid electrolyte interphase (SEI) formation, conceptual models, and advanced real-time characterizations of LMI are presented. Instructed by the conceptual models, strategies including increasing the donatable fluorine concentration (DFC) in liquid to enrich LiF component in SEI, increasing salt concentration (ionic strength) and sacrificial electrolyte additives, building artificial SEI to boost self-healing of natural SEI, and 3D electrode frameworks to reduce current density and delay Sand's extinction are summarized. Practical challenges in competing with graphite and silicon anodes are outlined. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical modification of electrolytes for lithium batteries

NASA Astrophysics Data System (ADS)

Afanas'ev, Vladimir N.; Grechin, Aleksandr G.

2002-09-01

Modern approaches to modifying chemically electrolytes for lithium batteries are analysed with the aim of optimising the charge-transfer processes in liquid-phase and solid (polymeric) media. The main regularities of transport properties of lithium electrolyte solutions containing complex (encapsulated) ions in aprotic solvents and polymers are discussed. The prospects for the development of electrolytic solvosystems with the chain (ionotropic) mechanism of conduction with respect to lithium ions are outlined. The bibliography includes 126 references.

Using liquid and solid state NMR and photoluminescence to study the synthesis and solubility properties of amine capped silicon nanoparticles.

PubMed

Giuliani, J R; Harley, S J; Carter, R S; Power, P P; Augustine, M P

2007-08-01

Water soluble silicon nanoparticles were prepared by the reaction of bromine terminated silicon nanoparticles with 3-(dimethylamino)propyl lithium and characterized with liquid and solid state nuclear magnetic resonance (NMR) and photoluminescence (PL) spectroscopies. The surface site dependent 29Si chemical shifts and the nuclear spin relaxation rates from an assortment of 1H-29Si heteronuclear solid state NMR experiments for the amine coated reaction product are consistent with both the 1H and 13C liquid state NMR results and routine transmission electron microscopy, ultra-violet/visible, and Fourier transform infrared measurements. PL was used to demonstrate the pH dependent solubility properties of the amine passivated silicon nanoparticles.

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.

Heteroaromatic-based electrolytes for lithium and lithium-ion batteries

DOEpatents

Cheng, Gang; Abraham, Daniel P.

2017-04-18

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

Extraction of Li and Co from Li-ion Batteries by Chemical Methods

NASA Astrophysics Data System (ADS)

Guzolu, Jafar Sharrivar; Gharabaghi, Mahdi; Mobin, Mohammad; Alilo, Hojat

2017-04-01

In this work a process involving ultrasonic washing and leaching and precipitation was used to recover Li and Co from spent Li-ion batteries. Ultrasonic washing was used to reduce energy consumption and pollution whereas hydrochloric acid was used as leaching reagent. 98 % of Li and nearly 99 % of Co were obtained under optimum condition of 5 M hydrochloric acid solution, temperature of 95 °C, reaction time of 70 min, and solid-liquid ratio of 10 g/L. In this process at first nickel, copper, iron, aluminum, cobalt, and manganese were precipitated from leaching solution using sodium hydroxide at pH f 12.5 and reaction time of 1 h and temperature was 55 °C and all metal recoveries were more than 99 %. In the precipitation experiments, lithium loss was only 18.34 %. In the next stage, white lithium carbonate was precipitated by addition of saturated sodium carbonate solution to the left filtrate from first precipitation step. The purity of the recovered powder of lithium was 95 %.

A flowing liquid lithium limiter for the Experimental Advanced Superconducting Tokamak

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

Ren, J.; Zuo, G. Z.; Hu, J. S.

2015-02-15

A program involving the extensive and systematic use of lithium (Li) as a “first,” or plasma-facing, surface in Tokamak fusion research devices located at Institute of Plasma Physics, Chinese Academy of Sciences, was started in 2009. Many remarkable results have been obtained by the application of Li coatings in Experimental Advanced Superconducting Tokamak (EAST) and liquid Li limiters in the HT-7 Tokamak—both located at the institute. In furtherance of the lithium program, a flowing liquid lithium (FLiLi) limiter system has been designed and manufactured for EAST. The design of the FLiLi limiter is based on the concept of a thinmore » flowing film which was previously tested in HT-7. Exploiting the capabilities of the existing material and plasma evaluation system on EAST, the limiter will be pre-wetted with Li and mechanically translated to the edge of EAST during plasma discharges. The limiter will employ a novel electro-magnetic pump which is designed to drive liquid Li flow from a collector at the bottom of limiter into a distributor at its top, and thus supply a continuously flowing liquid Li film to the wetted plasma-facing surface. This paper focuses on the major design elements of the FLiLi limiter. In addition, a simulation of incoming heat flux has shown that the distribution of heat flux on the limiter surface is acceptable for a future test of power extraction on EAST.« less

Branched Rod-Coil Polyimide-Poly(Alkylene Oxide) Copolymers and Electrolyte Compositions

NASA Technical Reports Server (NTRS)

Meador, Maryann B. (Inventor); Tigelaar, Dean M. (Inventor)

2014-01-01

Crosslinked polyimide-poly(alkylene oxide) copolymers capable of holding large volumes of liquid while maintaining good dimensional stability. Copolymers are derived at ambient temperatures from amine endcapped amic-acid oligomers subsequently imidized in solution at increased temperatures, followed by reaction with trifunctional compounds in the presence of various additives. Films of these copolymers hold over four times their weight at room temperature of liquids such as ionic liquids (RTIL) and/or carbonate solvents. These rod-coil polyimide copolymers are used to prepare polymeric electrolytes by adding to the copolymers various amounts of compounds such as ionic liquids (RTIL), lithium trifluoromethane-sulfonimide (LiTFSi) or other lithium salts, and alumina.

Dendrite-Free Electrodeposition and Reoxidation of Lithium-Sodium Alloy for Metal-Anode Battery

DTIC Science & Technology

2011-11-01

Dendrite-Free Electrodeposition and Reoxidation of Lithium-Sodium Alloy for Metal-Anode Battery Johanna K. Star 1 , Yi Ding 2 , and Paul A. Kohl ,1, * 1...Journal Article 3. DATES COVERED 01-11-2011 to 01-11-2011 4. TITLE AND SUBTITLE DENDRITE-FREE ELECTRODEPOSITION AND REOXIDATION OF LITHIUM-SODIUM...Results and Discussion The initial ionic liquid selection was driven by the need to electrodeposit sodium and lithium from the same electrolyte

Ionic Liquids as a Medium for Ionic Chain Polymerizations: An Environmentally Responsible Approach to Macromolecular Synthesis with Controlled Architecture

DTIC Science & Technology

2004-09-16

published in non peer-reviewed journals: 1. Gross, SM, Hamilton JL. "Polymer Gels for Use in Lithium Polymer Batteries", Nebraska Academy of Science...a process for the anionic polymerization of styrene and methyl methacrylate in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ...Current polymer electrolyte composites used for these applications typically comprise polyethers with ethylene carbonate solvents containing lithium

Molecular dynamics simulations of bubble formation and cavitation in liquid metals.

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

Insepov, Z.; Hassanein, A.; Bazhirov, T. T.

2007-11-01

Thermodynamics and kinetics of nano-scale bubble formation in liquid metals such as Li and Pb were studied by molecular dynamics (MD) simulations at pressures typical for magnetic and inertial fusion. Two different approaches to bubble formation were developed. In one method, radial densities, pressures, surface tensions, and work functions of the cavities in supercooled liquid lithium were calculated and compared with the surface tension experimental data. The critical radius of a stable cavity in liquid lithium was found for the first time. In the second method, the cavities were created in the highly stretched region of the liquid phase diagram;more » and then the stability boundary and the cavitation rates were calculated in liquid lead. The pressure dependences of cavitation frequencies were obtained over the temperature range 700-2700 K in liquid Pb. The results of MD calculations for cavitation rate were compared with estimates of classical nucleation theory (CNT).« less

Method and apparatus to produce and maintain a thick, flowing, liquid lithium first wall for toroidal magnetic confinement DT fusion reactors

DOEpatents

Woolley, Robert D.

2002-01-01

A system for forming a thick flowing liquid metal, in this case lithium, layer on the inside wall of a toroid containing the plasma of a deuterium-tritium fusion reactor. The presence of the liquid metal layer or first wall serves to prevent neutron damage to the walls of the toroid. A poloidal current in the liquid metal layer is oriented so that it flows in the same direction as the current in a series of external magnets used to confine the plasma. This current alignment results in the liquid metal being forced against the wall of the toroid. After the liquid metal exits the toroid it is pumped to a heat extraction and power conversion device prior to being reentering the toroid.

Edge properties with the liquid lithium limiter in FTU—experiment and transport modelling

NASA Astrophysics Data System (ADS)

Pericoli-Ridolfini, V.; Apicella, M. L.; Mazzitelli, G.; Tudisco, O.; Zagórski, R.; FTU Team

2007-07-01

Liquid lithium as a plasma-facing material was tested for the first time on a high field medium size tokamak, FTU. A liquid Li reservoir supplies a mesh of capillaries that is movable from shot to shot in the scrape-off layer (SOL) plasma to act as a secondary limiter. An almost complete lithization of the vacuum vessel walls is obtained in about three discharges. Plasmas cleaner than boronization and titanization, with lower radiation losses and smaller impurity content are produced. The SOL electron temperature increases, ΔTe ~ 10 eV, while density (ne) is less affected. The 2D multifluid code TECXY explains this only if a strong reduction of plasma recycling on the walls and main limiter occurs, consistent with the high Li hydrogen pumping capability. This property also permits a much tighter control of the plasma density. With the Li limiter inserted inside the vessel poloidal asymmetries develop in the SOL that TECXY explains with a local increase of radiation, caused by enhanced evaporation/sputtering of Li. New regimes can be produced in such conditions with a clear increase in |∇ne/ne| and of the peaking factor ne0/

Liquid surface skimmer apparatus for molten lithium and method

DOEpatents

Robinson, Samuel C.; Pollard, Roy E.; Thompson, William F.; Stark, Marshall W.; Currin, Jr., Robert T.

1995-01-01

This invention relates to an apparatus for separating two fluids having different specific gravities. The invention also relates to a method for using the separating apparatus of the present invention. This invention particularly relates to the skimming of molten lithium metal from the surface of a fused salt electrolyte in the electrolytic production of lithium metal from a mixed fused salt.

The Twentieth International Symposium on Molten Salts and Ionic Liquids

DTIC Science & Technology

2016-11-29

Heterocyclic Carbene Involved?" by Hyung Kim "Carbon Dioxide Absorption Behavior and Cabronate Ion Transport of Lithium Orthosilicate/Molten Carbonate...K. Gemmell, K. Johnson, A. East 575 Lithium Ion Conduction in Single Lithium Perfluorosulfonylamides K. Kubota, H. Matsumoto 585...energy applications (e.g., batteries , fuel cells, semiconductors, photovoltaics, and phase change energy storage); (3) rare earth and nuclear chemistry

Lithium/organosulfur redox cell having protective solid electrolyte barrier formed on anode and method of making same

DOEpatents

De Jonghe, Lutgard C.; Visco, Steven J.; Liu, Meilin; Mailhe, Catherine C.

1990-01-01

A lithium/organosulfur redox cell is disclosed which comprises a solid lium anode, a liquid organosulfur cathode, and a barrier layer formed adjacent a surface of the solid lithium anode facing the liquid organosulfur cathode consisting of a reaction product of the lithium anode with the organosulfur cathode. The organosulfur cathode comprises a material having the formula (R(S).sub.y).sub.N where y=1 to 6, n=2 to 20 and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the linear chain may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

Effect of lithium salts addition on the ionic liquid based extraction of essential oil from Farfarae Flos.

PubMed

Li, Zhen-Yu; Zhang, Sha-Sha; Jie-Xing; Qin, Xue-Mei

2015-01-01

In this study, an ionic liquids (ILs) based extraction approach has been successfully applied to the extraction of essential oil from Farfarae Flos, and the effect of lithium chloride was also investigated. The results indicated that the oil yields can be increased by the ILs, and the extraction time can be reduced significantly (from 4h to 2h), compared with the conventional water distillation. The addition of lithium chloride showed different effect according to the structures of ILs, and the oil yields may be related with the structure of cation, while the chemical compositions of essential oil may be related with the anion. The reduction of extraction time and remarkable higher efficiency (5.41-62.17% improved) by combination of lithium salt and proper ILs supports the suitability of the proposed approach. Copyright © 2014 Elsevier B.V. All rights reserved.

Homogeneous lithium electrodeposition with pyrrolidinium-based ionic liquid electrolytes.

PubMed

Grande, Lorenzo; von Zamory, Jan; Koch, Stephan L; Kalhoff, Julian; Paillard, Elie; Passerini, Stefano

2015-03-18

In this study, we report on the electroplating and stripping of lithium in two ionic liquid (IL) based electrolytes, namely N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl) imide (Pyr14FSI) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI), and mixtures thereof, both on nickel and lithium electrodes. An improved method to evaluate the Li cycling efficiency confirmed that homogeneous electroplating (and stripping) of Li is possible with TFSI-based ILs. Moreover, the presence of native surface features on lithium, directly observable via scanning electron microscope imaging, was used to demonstrate the enhanced electrolyte interphase (SEI)-forming ability, that is, fast cathodic reactivity of this class of electrolytes and the suppressed dendrite growth. Finally, the induced inhomogeneous deposition enabled us to witness the SEI cracking and revealed previously unreported bundled Li fibers below the pre-existing SEI and nonrod-shaped protuberances resulting from Li extrusion.

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin Bradley; Bennett, William Raymond; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W., Jr.; Watson, John W.

2014-01-01

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI] and [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bennett, William R.; Hernandez-Lugo, Dione M.; Wu, James; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

2014-01-01

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-Npropylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of x(sub Li) we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing x(sub Li), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of x(sub Li) is approximately 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 - 0.3 mS/cm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

Enhancing effects of chronic lithium on memory in the rat.

PubMed

Tsaltas, Eleftheria; Kontis, Dimitrios; Boulougouris, Vasileios; Papakosta, Vasiliki-Maria; Giannou, Haralambos; Poulopoulou, Cornelia; Soldatos, Constantine

2007-02-12

In spite of recent enrichment of neurochemical and behavioural data establishing a neuroprotective role for lithium, its primary effects on cognitive functioning remain ambiguous. This study examines chronic lithium effects on spatial working memory and long-term retention. In three discrete experiments, rats subjected to 30 daily intraperitoneal injections (2mmol/kg) of lithium (lithium groups: serum lithium=0.5+/-0.4mEq/l, 12h post-injection) or saline (controls) were trained in 0-s delay T-maze alternation and then tested in 30-, 45- and 60-s delay alternation (Experiments 1, 2, 3, respectively). Animals from Experiment 1 were further tested in one-trial step-through passive avoidance under mild shock parameters (0.5mA, 1s). Retention was assessed 6h later. Daily lithium or saline injections continued throughout behavioural testing. Lithium animals were indistinguishable from controls during 0-delay alternation baseline (Experiments 1-3, accuracy>88%) but showed significantly higher accuracy than controls at 30- and 45-s delays (93% versus 85% and 92% versus 82%, Experiments 1 and 2, respectively). At 60-s delay (Experiment 3) this beneficial effect of lithium was no longer apparent (lithium and control accuracy=78%). In Experiment 4, the shock used did not support 6-h passive avoidance retention in controls, whereas lithium animals showed significant step-through latency increases. Chronic lithium enhanced spatial working memory and promoted long-term retention of a weak aversive contingency. The results suggest that lithium may have potential as a cognitive enhancer.

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.

Synergistic effects of mixing sulfone and ionic liquid as safe electrolytes for lithium sulfur batteries.

PubMed

Liao, Chen; Guo, Bingkun; Sun, Xiao-Guang; Dai, Sheng

2015-01-01

A strategy of mixing both an ionic liquid and sulfone is reported to give synergistic effects of reducing viscosity, increasing ionic conductivity, reducing polysulfide dissolution, and improving safety. The mixtures of ionic liquids and sulfones also show distinctly different physicochemical properties, including thermal properties and crystallization behavior. By using these electrolytes, lithium sulfur batteries assembled with lithium and mesoporous carbon composites show a reversible specific capacity of 1265 mAh g(-1) (second cycle) by using 40 % 1.0 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide with 60 % 1.0 M LiTFSI in methylisopropylsulfone in the first cycle. This capacity is slightly lower than that obtained in pure 1.0 M LiTFSI as the sulfone electrolyte; however, it exhibits excellent cycling stability and remains as high as 655 mAh g(-1) even after 50 cycles. This strategy provides a method to alleviate polysulfide dissolution and redox shuttle phenomena, at the same time, with improved ionic conductivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operando characterization of cathodic reactions in a liquid-state lithium-oxygen micro-battery by scanning transmission electron microscopy.

PubMed

Liu, Pan; Han, Jiuhui; Guo, Xianwei; Ito, Yoshikazu; Yang, Chuchu; Ning, Shoucong; Fujita, Takeshi; Hirata, Akihiko; Chen, Mingwei

2018-02-16

Rechargeable non-aqueous lithium-oxygen batteries with a large theoretical capacity are emerging as a high-energy electrochemical device for sustainable energy strategy. Despite many efforts made to understand the fundamental Li-O 2 electrochemistry, the kinetic process of cathodic reactions, associated with the formation and decomposition of a solid Li 2 O 2 phase during charging and discharging, remains debate. Here we report direct visualization of the charge/discharge reactions on a gold cathode in a non-aqueous lithium-oxygen micro-battery using liquid-cell aberration-corrected scanning transmission electron microscopy (STEM) combining with synchronized electrochemical measurements. The real-time and real-space characterization by time-resolved STEM reveals the electrochemical correspondence of discharge/charge overpotentials to the nucleation, growth and decomposition of Li 2 O 2 at a constant current density. The nano-scale operando observations would enrich our knowledge on the underlying reaction mechanisms of lithium-oxygen batteries during round-trip discharging and charging and shed lights on the strategies in improving the performances of lithium-oxygen batteries by tailoring the cathodic reactions.

New Ether-functionalized Morpholinium- and Piperidinium-based Ionic Liquids as Electrolyte Components in Lithium and Lithium-Ion Batteries.

PubMed

Navarra, Maria Assunta; Fujimura, Kanae; Sgambetterra, Mirko; Tsurumaki, Akiko; Panero, Stefania; Nakamura, Nobuhumi; Ohno, Hiroyuki; Scrosati, Bruno

2017-06-09

Here, two ionic liquids, N-ethoxyethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide (M 1,2O2 TFSI) and N-ethoxyethyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide (P 1,2O2 TFSI) were synthesized and compared. Fundamental relevant properties, such as thermal and electrochemical stability, density, and ionic conductivity were analyzed to evaluate the effects caused by the presence of the ether bond in the side chain and/or in the organic cation ring. Upon lithium salt addition, two electrolytes suitable for lithium batteries applications were found. Higher conducting properties of the piperidinium-based electrolyte resulted in enhanced cycling performances when tested with LiFePO 4 (LFP) cathode in lithium cells. When mixing the P 1,2O2 TFSI/LiTFSI electrolyte with a tailored alkyl carbonate mixture, the cycling performance of both Li and Li-ion cells greatly improved, with prolonged cyclability delivering very stable capacity values, as high as the theoretical one in the case of Li/LFP cell configurations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlled Synthesis and Functionalization of Vertically-Aligned Carbon Nanotubes for Multifunctional Applications

DTIC Science & Technology

2015-05-07

6 1.6 Lithium - Ion Batteries Based on Vertically-Aligned Carbon Nanotube Electrodes and Ionic...Cl, Br, or I) Prepared by Ball-Milling and Used as Anode Materials for Lithium - Ion Batteries ……………....................23 3.4 Well-Defined Two...9 1.6 Lithium - Ion Batteries Based on Vertically-Aligned Carbon Nanotube Electrodes and Ionic Liquid Electrolytes

Solid-Liquid Lithium Electrolyte Nanocomposites Derived from Porous Molecular Cages.

PubMed

Petronico, Aaron; Moneypenny, Timothy P; Nicolau, Bruno G; Moore, Jeffrey S; Nuzzo, Ralph G; Gewirth, Andrew A

2018-06-20

We demonstrate that solid-liquid nanocomposites derived from porous organic cages are effective lithium ion electrolytes at room temperature. A solid-liquid electrolyte nanocomposite (SLEN) fabricated from a LiTFSI/DME electrolyte system and a porous organic cage exhibits ionic conductivity on the order of 1 × 10 -3 S cm -1 . With an experimentally measured activation barrier of 0.16 eV, this composite is characterized as a superionic conductor. Furthermore, the SLEN displays excellent oxidative stability up to 4.7 V vs Li/Li + . This simple three-component system enables the rational design of electrolytes from tunable discrete molecular architectures.

Imidazolium-based Block Copolymers as Solid-State Separators for Alkaline Fuel Cells and Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Nykaza, Jacob Richard

In this study, polymerized ionic liquid (PIL) diblock copolymers were explored as solid-state polymer separators as an anion exchange membrane (AEM) for alkaline fuel cells AFCs and as a solid polymer electrolyte (SPE) for lithium-ion batteries. Polymerized ionic liquid (PIL) block copolymers are a distinct set of block copolymers that combine the properties of both ionic liquids (e.g., high conductivity, high electrochemical stability) and block copolymers (e.g., self-assembly into various nanostructures), which provides the opportunity to design highly conductive robust solid-state electrolytes that can be tuned for various applications including AFCs and lithium-ion batteries via simple anion exchange. A series of bromide conducting PIL diblock copolymers with an undecyl alkyl side chain between the polymer backbone and the imidazolium moiety were first synthesized at various compositions comprising of a PIL component and a non-ionic component. Synthesis was achieved by post-functionalization from its non-ionic precursor PIL diblock copolymer, which was synthesized via the reverse addition fragmentation chain transfer (RAFT) technique. This PIL diblock copolymer with long alkyl side chains resulted in flexible, transparent films with high mechanical strength and high bromide ion conductivity. The conductivity of the PIL diblock copolymer was three times higher than its analogous PIL homopolymer and an order of magnitude higher than a similar PIL diblock copolymer with shorter alkyl side chain length, which was due to the microphase separated morphology, more specifically, water/ion clusters within the PIL microdomains in the hydrated state. Due to the high conductivity and mechanical robustness of this novel PIL block copolymer, its application as both the ionomer and AEM in an AFC was investigated via anion exchange to hydroxide (OH-), where a maximum power density of 29.3 mW cm-1 (60 °C with H2/O2 at 25 psig (172 kPa) backpressure) was achieved. Rotating disk electrode (RDE) experiments determined the interfacial resistance imposed during cell assembly between the AEM, catalyst, and ionomer was a factor in fuel cell performance. Further RDE studies investigated the electrochemical stability of the PIL block copolymer ionomer under applied potentials, where it was determined that potential cycling increased the degradation compared to constant voltage or open circuit voltage studies. The PIL diblock copolymer was then anion exchanged to the bis(trifluoromethane)sulfonamide (TFSI-) anion form and imbibed with a lithium salt and ionic liquid solution for use as a SPE in lithium-ion batteries resulting in a maximum discharge capacity of 112 mAh g-1 at 0.1 C with a Coulombic efficiency greater than 94% over 100 cycles. PIL block copolymers have promising mechanical properties and transport properties (i.e., ion conductivity) in both the hydrated (hydrophilic anions; Br-, OH-) and dry (hydrophobic anions; TFSI-) states resulting in highly conductive, chemically/thermally stable, and mechanically robust solid-state polymer separators for use as AEMs in AFCs and as SPEs in lithium-ion batteries.

Lithium As Plasma Facing Component for Magnetic Fusion Research

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

Masayuki Ono

The use of lithium in magnetic fusion confinement experiments started in the 1990's in order to improve tokamak plasma performance as a low-recycling plasma-facing component (PFC). Lithium is the lightest alkali metal and it is highly chemically reactive with relevant ion species in fusion plasmas including hydrogen, deuterium, tritium, carbon, and oxygen. Because of the reactive properties, lithium can provide strong pumping for those ions. It was indeed a spectacular success in TFTR where a very small amount (~ 0.02 gram) of lithium coating of the PFCs resulted in the fusion power output to improve by nearly a factor ofmore » two. The plasma confinement also improved by a factor of two. This success was attributed to the reduced recycling of cold gas surrounding the fusion plasma due to highly reactive lithium on the wall. The plasma confinement and performance improvements have since been confirmed in a large number of fusion devices with various magnetic configurations including CDX-U/LTX (US), CPD (Japan), HT-7 (China), EAST (China), FTU (Italy), NSTX (US), T-10, T-11M (Russia), TJ-II (Spain), and RFX (Italy). Additionally, lithium was shown to broaden the plasma pressure profile in NSTX, which is advantageous in achieving high performance H-mode operation for tokamak reactors. It is also noted that even with significant applications (up to 1,000 grams in NSTX) of lithium on PFCs, very little contamination (< 0.1%) of lithium fraction in main fusion plasma core was observed even during high confinement modes. The lithium therefore appears to be a highly desirable material to be used as a plasma PFC material from the magnetic fusion plasma performance and operational point of view. An exciting development in recent years is the growing realization of lithium as a potential solution to solve the exceptionally challenging need to handle the fusion reactor divertor heat flux, which could reach 60 MW/m2 . By placing the liquid lithium (LL) surface in the path of the main divertor heat flux (divertor strike point), the lithium is evaporated from the surface. The evaporated lithium is quickly ionized by the plasma and the ionized lithium ions can provide a strongly radiative layer of plasma ("radiative mantle"), thus could significantly reduce the heat flux to the divertor strike point surfaces, thus protecting the divertor surface. The protective effects of LL have been observed in many experiments and test stands. As a possible reactor divertor candidate, a closed LL divertor system is described. Finally, it is noted that the lithium applications as a PFC can be quite flexible and broad. The lithium application should be quite compatible with various divertor configurations, and it can be also applied to protecting the presently envisioned tungsten based solid PFC surfaces such as the ones for ITER. Lithium based PFCs therefore have the exciting prospect of providing a cost effective flexible means to improve the fusion reactor performance, while providing a practical solution to the highly challenging divertor heat handling issue confronting the steadystate magnetic fusion reactors.« less

Cation effect on small phosphonium based ionic liquid electrolytes with high concentrations of lithium salt

NASA Astrophysics Data System (ADS)

Chen, Fangfang; Kerr, Robert; Forsyth, Maria

2018-05-01

Ionic liquid electrolytes with high alkali salt concentrations have displayed some excellent electrochemical properties, thus opening up the field for further improvements to liquid electrolytes for lithium or sodium batteries. Fundamental computational investigations into these high concentration systems are required in order to gain a better understanding of these systems, yet they remain lacking. Small phosphonium-based ionic liquids with high concentrations of alkali metal ions have recently shown many promising results in experimental studies, thereby prompting us to conduct further theoretical exploration of these materials. Here, we conducted a molecular dynamics simulation on four small phosphonium-based ionic liquids with 50 mol. % LiFSI salt, focusing on the effect of cation structure on local structuring and ion diffusional and rotational dynamics—which are closely related to the electrochemical properties of these materials.

An advanced lithium-air battery exploiting an ionic liquid-based electrolyte.

PubMed

Elia, G A; Hassoun, J; Kwak, W-J; Sun, Y-K; Scrosati, B; Mueller, F; Bresser, D; Passerini, S; Oberhumer, P; Tsiouvaras, N; Reiter, J

2014-11-12

A novel lithium-oxygen battery exploiting PYR14TFSI-LiTFSI as ionic liquid-based electrolyte medium is reported. The Li/PYR14TFSI-LiTFSI/O2 battery was fully characterized by electrochemical impedance spectroscopy, capacity-limited cycling, field emission scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The results of this extensive study demonstrate that this new Li/O2 cell is characterized by a stable electrode-electrolyte interface and a highly reversible charge-discharge cycling behavior. Most remarkably, the charge process (oxygen oxidation reaction) is characterized by a very low overvoltage, enhancing the energy efficiency to 82%, thus, addressing one of the most critical issues preventing the practical application of lithium-oxygen batteries.

Ionic liquid electrolytes for Li-air batteries: lithium metal cycling.

PubMed

Grande, Lorenzo; Paillard, Elie; Kim, Guk-Tae; Monaco, Simone; Passerini, Stefano

2014-05-08

In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li-air cells.

Ionic Liquid Electrolytes for Li–Air Batteries: Lithium Metal Cycling

PubMed Central

Grande, Lorenzo; Paillard, Elie; Kim, Guk-Tae; Monaco, Simone; Passerini, Stefano

2014-01-01

In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li–air cells. PMID:24815072

Composite anode for lithium ion batteries

DOEpatents

de Guzman, Rhet C.; Ng, K.Y. Simon; Salley, Steven O.

2018-03-06

A composite anode for a lithium-ion battery is manufactured from silicon nanoparticles having diameters mostly under 10 nm; providing an oxide layer on the silicon nanoparticles; dispersing the silicon nanoparticles in a polar liquid; providing a graphene oxide suspension; mixing the polar liquid containing the dispersed silicone nanoparticles with the graphene oxide suspension to obtain a composite mixture; probe-sonicating the mixture for a predetermined time; filtering the composite mixture to obtain a solid composite; drying the composite; and reducing the composite to obtain graphene and silicon.

Realisation of an all solid state lithium battery using solid high temperature plastic crystal electrolytes exhibiting liquid like conductivity.

PubMed

Shekibi, Youssof; Rüther, Thomas; Huang, Junhua; Hollenkamp, Anthony F

2012-04-07

Replacement of volatile and combustible electrolytes in conventional lithium batteries is desirable for two reasons: safety concerns and increase in specific energy. In this work we consider the use of an ionic organic plastic crystal material (IOPC), N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF(4)], as a solid-state electrolyte for lithium battery applications. The effect of inclusion of 1 to 33 mol% lithium tetrafluoroborate, LiBF(4), into [C2mpyr][BF(4)] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, cyclic voltammetry and cycling of full Li|LiFePO(4) batteries. The increases in ionic conductivity by orders of magnitude observed at higher temperature are most likely associated with an increase in Li ion mobility in the highest plastic phase. At concentrations >5 mol% LiBF(4) the ionic conductivity of these solid-state composites is comparable to the ionic conductivity of room temperature ionic liquids. Galvanostatic cycling of Li|Li symmetrical cells showed that the reversibility of the lithium metal redox reaction at the interface of this plastic crystal electrolyte is sufficient for lithium battery applications. For the first time we demonstrate an all solid state lithium battery incorporating solid electrolytes based on IOPC as opposed to conventional flammable organic solvents.

Solvent-directed Solgel Assembly of 3-dimensional Graphene-tented Metal Oxides and Strong Synergistic Disparities in Lithium Storage

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

Ye, Jianchao C.; An, Yonghao H.; Montalvo, Elizabeth

The graphene/metal oxide (GMO) nanocomposites promise a broad range of utilities for lithium ion batteries (LIBs), pseudocapacitors, catalysts, and sensors. When applied as anodes for LIBs, GMOs often exhibit high capacity, improved rate capability and cycling performance. Numerous studies have attributed these favorable properties to the charisma of graphene in assisting various metal oxides (MOs) to achieve near-theoretical capacities, exploiting the exceptional electronic and mechanical properties of graphene. By comparison, the true lithium storage mechanisms of graphene and their correlations with MOs remain enigmatic. Via a unique two-step liquid-flow-guided solgel process, we have synthesized and investigated the electrochemical performance ofmore » several representative GMOs, namely Fe2O3/graphene, SnO2/graphene, and TiO2/graphene. We observe that MOs play an equally important role in promoting graphene to achieve large reversible lithium storage capacity. Our experiments suggest that the unexpected lithium storage heightening may arise from a unique surface coverage mechanism of MOs. The magnitude of capacity improvement is found to scale crudely with the surface coverage of MOs but depend strongly upon the storage mechanisms of MOs variety. Importantly, synergistic effect is only observed in conversion reaction GMOs (i.e., Fe2O3/graphene and SnO2/graphene) but not in intercalationbased GMOs (i.e., TiO2/graphene). Our first principles calculations suggest an alternative lithium storage sites from resultant interfaces between Li2O and graphene that agree with our experimental observations. This unusually beneficial role of MOs to graphene suggests an effective pathway for reversible lithium storage in graphene and shifts design paradigms for graphene-based electrodes.« less

Solvent-directed Solgel Assembly of 3-dimensional Graphene-tented Metal Oxides and Strong Synergistic Disparities in Lithium Storage

DOE PAGES

Ye, Jianchao C.; An, Yonghao H.; Montalvo, Elizabeth; ...

2016-02-10

The graphene/metal oxide (GMO) nanocomposites promise a broad range of utilities for lithium ion batteries (LIBs), pseudocapacitors, catalysts, and sensors. When applied as anodes for LIBs, GMOs often exhibit high capacity, improved rate capability and cycling performance. Numerous studies have attributed these favorable properties to the charisma of graphene in assisting various metal oxides (MOs) to achieve near-theoretical capacities, exploiting the exceptional electronic and mechanical properties of graphene. By comparison, the true lithium storage mechanisms of graphene and their correlations with MOs remain enigmatic. Via a unique two-step liquid-flow-guided solgel process, we have synthesized and investigated the electrochemical performance ofmore » several representative GMOs, namely Fe2O3/graphene, SnO2/graphene, and TiO2/graphene. We observe that MOs play an equally important role in promoting graphene to achieve large reversible lithium storage capacity. Our experiments suggest that the unexpected lithium storage heightening may arise from a unique surface coverage mechanism of MOs. The magnitude of capacity improvement is found to scale crudely with the surface coverage of MOs but depend strongly upon the storage mechanisms of MOs variety. Importantly, synergistic effect is only observed in conversion reaction GMOs (i.e., Fe2O3/graphene and SnO2/graphene) but not in intercalationbased GMOs (i.e., TiO2/graphene). Our first principles calculations suggest an alternative lithium storage sites from resultant interfaces between Li2O and graphene that agree with our experimental observations. This unusually beneficial role of MOs to graphene suggests an effective pathway for reversible lithium storage in graphene and shifts design paradigms for graphene-based electrodes.« less

Ion Transport and Structural Properties of Polymeric Electrolytes and Ionic Liquids from Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Borodin, Oleg

2010-03-01

Molecular dynamics simulations are well suited for exploring electrolyte structure and ion transport mechanisms on the nanometer length scale and the nanosecond time scales. In this presentation we will describe how MD simulations assist in answering fundamental questions about the lithium transport mechanisms in polymeric electrolytes and ionic liquids. In particular, in the first part of the presentation the extent of ion aggregation, the structure of ion aggregates and the lithium cation diffusion in binary polymeric electrolytes will be compared with that of single-ion conducting polymers. In the second part of the talk, the lithium transport in polymeric electrolytes will be compared with that of three ionic liquids ( [emim][FSI] doped with LiFSI , [pyr13][FSI] doped with LiFSI, [emim][BF4] doped with LiBF4). The relation between ionic liquid self-diffusion, conductivity and thermodynamic properties will be discussed in details. A number of correlations between heat of vaporization Hvap, cation-anion binding energy (E+/-), molar volume (Vm), self-diffusion coefficient (D) and ionic conductivity for 29 ionic liquids have been investigated using MD simulations. A significant correlation between D and Hvap has been found, while best correlation was found for -log((D Vm)) vs. Hvap+0.28E+/-. A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids.

Ceramic-metal seals for advanced battery systems. [sodium sulfur and lithium sulfur batteries

NASA Technical Reports Server (NTRS)

Reed, L.

1978-01-01

The search for materials which are electrochemically compatible with the lithium sulfur and sodium sulfur systems is discussed. The use liquid or braze alloys, titanium hydrite coatings, and tungsten yttria for bonding beryllium with ceramic is examined.

Electrochemical Capacities of Commercially Available Structural Carbon Fibers, Fabrics, and Papers

DTIC Science & Technology

2008-09-01

Hollingsworth & Vose. A liquid electrolyte of ethylene carbonate: ethyl methyl carbonate (3:7 by weight) with 1.0 M lithium hexafluorophosphate (LiPF6) was...fiber pulp COTS commercial off-the-shelf Da dalton FE-SEM Field Emission Scanning Electron Microscope LiPF6 lithium hexafluorophosphate MWNT...material for anodes in modern technologies, particularly in lithium -ion batteries and electrochemical supercapacitors. Graphitic carbon allows for

Hot filament technique for measuring the thermal conductivity of molten lithium fluoride

NASA Technical Reports Server (NTRS)

Jaworske, Donald A.; Perry, William D.

1990-01-01

Molten salts, such as lithium fluoride, are attractive candidates for thermal energy storage in solar dynamic space power systems because of their high latent heat of fusion. However, these same salts have poor thermal conductivities which inhibit the transfer of heat into the solid phase and out of the liquid phase. One concept for improving the thermal conductivity of the thermal energy storage system is to add a conductive filler material to the molten salt. High thermal conductivity pitch-based graphite fibers are being considered for this application. Although there is some information available on the thermal conductivity of lithium fluoride solid, there is very little information on lithium fluoride liquid, and no information on molten salt graphite fiber composites. This paper describes a hot filament technique for determining the thermal conductivity of molten salts. The hot filament technique was used to find the thermal conductivity of molten lithium fluoride at 930 C, and the thermal conductivity values ranged from 1.2 to 1.6 W/mK. These values are comparable to the slightly larger value of 5.0 W/mK for lithium fluoride solid. In addition, two molten salt graphite fiber composites were characterized with the hot filament technique and these results are also presented.

An approach of ionic liquids/lithium salts based microwave irradiation pretreatment followed by ultrasound-microwave synergistic extraction for two coumarins preparation from Cortex fraxini.

PubMed

Liu, Zaizhi; Gu, Huiyan; Yang, Lei

2015-10-23

Ionic liquids/lithium salts solvent system was successfully introduced into the separation technique for the preparation of two coumarins (aesculin and aesculetin) from Cortex fraxini. Ionic liquids/lithium salts based microwave irradiation pretreatment followed by ultrasound-microwave synergy extraction (ILSMP-UMSE) procedure was developed and optimized for the sufficient extraction of these two analytes. Several variables which can potentially influence the extraction yields, including pretreatment time and temperature, [C4mim]Br concentration, LiAc content, ultrasound-microwave synergy extraction (UMSE) time, liquid-solid ratio, and UMSE power were optimized by Plackett-Burman design. Among seven variables, UMSE time, liquid-solid ratio, and UMSE power were the statistically significant variables and these three factors were further optimized by Box-Behnken design to predict optimal extraction conditions and find out operability ranges with maximum extraction yields. Under optimum operating conditions, ILSMP-UMSE showed higher extraction yields of two target compounds than those obtained by reference extraction solvents. Method validation studies also evidenced that ILSMP-UMSE is credible for the preparation of two coumarins from Cortex fraxini. This study is indicative of the proposed procedure that has huge application prospects for the preparation of natural products from plant materials. Copyright © 2015 Elsevier B.V. All rights reserved.

A revolution in electrodes: recent progress in rechargeable lithium-sulfur batteries.

PubMed

Fang, Xin; Peng, Huisheng

2015-04-01

As a promising candidate for future batteries, the lithium-sulfur battery is gaining increasing interest due to its high capacity and energy density. However, over the years, lithium-sulfur batteries have been plagued by fading capacities and the low Coulombic efficiency derived from its unique electrochemical behavior, which involves solid-liquid transition reactions. Moreover, lithium-sulfur batteries employ metallic lithium as the anode, which engenders safety vulnerability of the battery. The electrodes play a pivotal role in the performance of lithium-sulfur batteries. A leap forward in progress of lithium-sulfur batteries is always accompanied by a revolution in the electrode technology. In this review, recent progress in rechargeable lithium-sulfur batteries is summarized in accordance with the evolution of the electrodes, including the diversified cathode design and burgeoning metallic-lithium-free anodes. Although the way toward application has still many challenges associated, recent progress in lithium-sulfur battery technology still paints an encouraging picture of a revolution in rechargeable batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid oxygen LOX compatibility evaluations of aluminum lithium (Al-Li) alloys: Investigation of the Alcoa 2090 and MMC weldalite 049 alloys

NASA Technical Reports Server (NTRS)

Diwan, Ravinder M.

1989-01-01

The behavior of liquid oxygen (LOX) compatibility of aluminum lithium (Al-Li) alloys is investigated. Alloy systems of Alcoa 2090, vintages 1 to 3, and of Martin Marietta Corporation (MMC) Weldalite 049 were evaluated for their behavior related to the LOX compatibility employing liquid oxygen impact test conditions under ambient pressures and up to 1000 psi. The developments of these aluminum lithium alloys are of critical and significant interest because of their lower densities and higher specific strengths and improved mechanical properties at cryogenic temperatures. Of the different LOX impact tests carried out at the Marshall Space Flight Center (MSFC), it is seen that in certain test conditions at higher pressures, not all Al-Li alloys are LOX compatible. In case of any reactivity, it appears that lithium makes the material more sensitive at grain boundaries due to microstructural inhomogeneities and associated precipitate free zones (PFZ). The objectives were to identify and rationalize the microstructural mechanisms that could be relaxed to LOX compatibility behavior of the alloy system in consideration. The LOX compatibility behavior of Al-Li 2090 and Weldalite 049 is analyzed in detail using microstructural characterization techniques with light optical metallography, scanning electron microscopy (SEM), electron microprobe analysis, and surface studies using secondary ion mass spectrometry (SIMS), electron spectroscopy in chemical analysis (ESCA) and Auger electron spectroscopy (AES). Differences in the behavior of these aluminum lithium alloys are assessed and related to their chemistry, heat treatment conditions, and microstructural effects.

Corrosion of V?Ti?Cr alloys in liquid lithium: influence of alloy composition and concentration of nitrogen in lithium

NASA Astrophysics Data System (ADS)

Eliseeva, O. I.; Fedirko, V. N.; Chernov, V. M.; Zavialsky, L. P.

2000-12-01

The effect of V-(0-70)Ti-(0-30)Cr (at.%) compositions on their compatibility with nitrogen-containing lithium (0.0015-0.67 at.% N) at 7000°C under steady-state test conditions and long-term contact with lithium (up to 2000 h) has been studied. The conditions for formation and stable coexistence of nitride layers on the surface of various compositions under variable nitrogen concentration in lithium have been defined. The V-(8-10)Ti-(4-5)Cr compositions showed the best characteristics from the standpoint of corrosion resistance, nitride layer stability under conditions of variable nitrogen concentration in lithium, and the possibility of 'in situ' protective nitride layer formation.

Ambient temperature secondary lithium cells containing inorganic electrolyte

NASA Astrophysics Data System (ADS)

Schlaikjer, Carl R.

The history and current status of rechargeable lithium cells using electrolytes based on liquid sulfur dioxide are reviewed. Three separate approaches currently under development include lithium/lithium dithionite/carbon cells with a supporting electrolyte salt; lithium/cupric chloride cells using sulfur dioxide/lithium tetrachloroaluminate; and several adaptations of a lithium/carbon cell using sulfur dioxide/lithium tetrachloroaluminate in which the discharge reaction involves the incorporation of aluminum into the positive electrode. The latter two chemistries have been studied in prototype hardware. For AA size cells with cupric chloride, 157 Whr/1 at 24 W/1 for 230 cycles was reported. For AA size cells containing 2LiCl-CaCl2-4AlCl3-12SO2, energy densities as high as 265 Whr/liter and 100 Whr/kg have been observed, but, at 26 W/1, for only 10 cycles. The advantages and remaining problems are discussed.

Safer Electrolytes for Lithium-Ion Cells

NASA Technical Reports Server (NTRS)

Kejha, Joe; Smith, Novis; McCloseky, Joel

2004-01-01

A number of nonvolatile, low-flammability liquid oligomers and polymers based on aliphatic organic carbonate molecular structures have been found to be suitable to be blended with ethylene carbonate to make electrolytes for lithium-ion electrochemical cells. Heretofore, such electrolytes have often been made by blending ethylene carbonate with volatile, flammable organic carbonates. The present nonvolatile electrolytes have been found to have adequate conductivity (about 2 mS/cm) for lithium ions and to remain liquid at temperatures down to -5 C. At normal charge and discharge rates, lithiumion cells containing these nonvolatile electrolytes but otherwise of standard design have been found to operate at current and energy densities comparable to those of cells now in common use. They do not perform well at high charge and discharge rates -- an effect probably attributable to electrolyte viscosity. Cells containing the nonvolatile electrolytes have also been found to be, variously, nonflammable or at least self-extinguishing. Hence, there appears to be a basis for the development of safer high-performance lithium-ion cells.

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

2007-01-01

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Advantages and Challenges of Radiative Liquid Lithium Divertor

NASA Astrophysics Data System (ADS)

Ono, Masayuki

2017-10-01

Steady-state fusion power plant designs present major divertor technology challenges, including high divertor heat flux both in steady-state and during transients. In addition to these concerns, there are the unresolved technology issues of long term dust accumulation and associated tritium inventory and safety issues. The application of lithium (Li) in NSTX resulted in improved H-mode confinement, H-mode power threshold reduction, and reduction in the divertor peak heat flux while maintaining essentially Li-free core plasma operation even during H-modes. These promising results in NSTX and related modeling calculations motivated the radiative liquid Li divertor (RLLD) concept and its variant, the active liquid Li divertor concept (ARLLD), taking advantage of the enhanced Li radiation in relatively poorly confined divertor plasmas. It has been suggested that radiation-based liquid lithium (LL) divertor concepts with a modest Li-loop could provide a possible solution for the outstanding fusion reactor technology issues such as divertor heat flux mitigation and real time dust removal, while potentially improving the reactor plasma performance. Laboratory tests are also planned to investigate the Li-T recover efficiency and other relevant research topics of the RLLD. This work supported by DoE Contract No. DE-AC02-09CH11466.

LiOH - H2O2 - H2O trinary system study for the selection of optimal conditions of lithium peroxide synthesis

NASA Astrophysics Data System (ADS)

Nefedov, R. A.; Ferapontov, Yu A.; Kozlova, N. P.

2016-01-01

Using solubility method the decay kinetics of peroxide products contained in liquid phase of LiOH - H2O2 - H2O trinary system with 2 to 6% by wt hydrogen peroxide content in liquid phase in 21 to 33 °C temperature range has been studied. Conducted studies have allowed to determine temperature and concentration limits of solid phase existence of Li2O2·H2O content, distinctness of which has been confirmed using chemical and qualitative X- ray phase analysis. Stabilizing effect of solid phase of Li2O2·H2O content on hydrogen peroxide decay contained in liquid phase of LiOH - H2O2 - H2O trinary system under conditions of experiments conducted has been shown.

Progress and prospect on failure mechanisms of solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Ma, Jun; Chen, Bingbing; Wang, Longlong; Cui, Guanglei

2018-07-01

By replacing traditional liquid organic electrolyte with solid-state electrolyte, the solid-state lithium batteries powerfully come back to the energy storage field due to their eminent safety and energy density. In recent years, a variety of solid-state lithium batteries based on excellent solid-state electrolytes are developed. However, the performance degradation of solid-state lithium batteries during cycling and storing is still a serious challenge for practical application. Therefore, this review summarizes the research progress of solid-state lithium batteries from the perspectives of failure phenomena and failure mechanisms. Additionally, the development of methodologies on studying the failure mechanisms of solid-state lithium batteries is also reviewed. Moreover, some perspectives on the remaining questions for understanding the failure behaviors and achieving long cycle life, high safety and high energy density solid-state lithium batteries are presented. This review will help researchers to recognize the status of solid-state lithium batteries objectively and attract much more research interest in conquering the failure issues of solid-state lithium batteries.

Nanostructured electrolytes for stable lithium electrodeposition in secondary batteries.

PubMed

Tu, Zhengyuan; Nath, Pooja; Lu, Yingying; Tikekar, Mukul D; Archer, Lynden A

2015-11-17

Secondary batteries based on lithium are the most important energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum. Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost of ceramic electrolytes that meet the modulus and stability requirements have to date proven to be insurmountable obstacles to progress. In this Account, we first review recent advances in continuum theory for dendrite growth and proliferation during metal electrodeposition. We show that the range of options for designing electrolytes and separators that stabilize electrodeposition is now substantially broader than one might imagine from previous literature accounts. In particular, separators designed at the nanoscale to constrain ion transport on length scales below a theory-defined cutoff, and structured electrolytes in which a fraction of anions are permanently immobilized to nanoparticles, to a polymer network or ceramic membrane are considered particularly promising for their ability to stabilize electrodeposition of lithium metal without compromising ionic conductivity or room temperature battery operation. We also review recent progress in designing surface passivation films for metallic lithium that facilitate fast deposition of lithium at the electrolyte/electrode interface and at the same time protect the lithium from parasitic side reactions with liquid electrolytes. A promising finding from both theory and experiment is that simple film-forming halide salt additives in a conventional liquid electrolyte can substantially extend the lifetime and safety of LMBs.

Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries

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

Tu, Zhengyuan; Nath, Pooja; Lu, Yingying

Secondary batteries based on lithium are the most important energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceousmore » host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum. Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost of ceramic electrolytes that meet the modulus and stability requirements have to date proven to be insurmountable obstacles to progress. In this Account, we first review recent advances in continuum theory for dendrite growth and proliferation during metal electrodeposition. We show that the range of options for designing electrolytes and separators that stabilize electrodeposition is now substantially broader than one might imagine from previous literature accounts. In particular, separators designed at the nanoscale to constrain ion transport on length scales below a theory-defined cutoff, and structured electrolytes in which a fraction of anions are permanently immobilized to nanoparticles, to a polymer network or ceramic membrane are considered particularly promising for their ability to stabilize electrodeposition of lithium metal without compromising ionic conductivity or room temperature battery operation. We also review recent progress in designing surface passivation films for metallic lithium that facilitate fast deposition of lithium at the electrolyte/electrode interface and at the same time protect the lithium from parasitic side reactions with liquid electrolytes. A promising finding from both theory and experiment is that simple film-forming halide salt additives in a conventional liquid electrolyte can substantially extend the lifetime and safety of LMBs.« less

Homogeneous fast-flux isotope-production reactor

DOEpatents

Cawley, W.E.; Omberg, R.P.

1982-08-19

A method is described for producing tritium in a liquid metal fast breeder reactor. Lithium target material is dissolved in the liquid metal coolant in order to facilitate the production and removal of tritium.

A high performance ceramic-polymer separator for lithium batteries

NASA Astrophysics Data System (ADS)

Kumar, Jitendra; Kichambare, Padmakar; Rai, Amarendra K.; Bhattacharya, Rabi; Rodrigues, Stanley; Subramanyam, Guru

2016-01-01

A three-layered (ceramic-polymer-ceramic) hybrid separator was prepared by coating ceramic electrolyte [lithium aluminum germanium phosphate (LAGP)] over both sides of polyethylene (PE) polymer membrane using electron beam physical vapor deposition (EB-PVD) technique. Ionic conductivities of membranes were evaluated after soaking PE and LAGP/PE/LAGP membranes in a 1 Molar (1M) lithium hexafluroarsenate (LiAsF6) electrolyte in ethylene carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) in volume ratio (1:1:1). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques were employed to evaluate morphology and structure of the separators before and after cycling performance tests to better understand structure-property correlation. As compared to regular PE separator, LAGP/PE/LAGP hybrid separator showed: (i) higher liquid electrolyte uptake, (ii) higher ionic conductivity, (iii) lower interfacial resistance with lithium and (iv) lower cell voltage polarization during lithium cycling at high current density of 1.3 mA cm-2 at room temperature. The enhanced performance is attributed to higher liquid uptake, LAGP-assisted faster ion conduction and dendrite prevention. Optimization of density and thickness of LAGP layer on PE or other membranes through manipulation of PVD deposition parameters will enable practical applications of this novel hybrid separator in rechargeable lithium batteries with high energy, high power, longer cycle life, and higher safety level.

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.

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.

Experimental investigation of MHD pressure losses in a mock-up of a liquid metal blanket

NASA Astrophysics Data System (ADS)

Mistrangelo, C.; Bühler, L.; Brinkmann, H.-J.

2018-03-01

Experiments have been performed to investigate the influence of a magnetic field on liquid metal flows in a scaled mock-up of a helium cooled lead lithium (HCLL) blanket. During the experiments pressure differences between points on the mock-up have been recorded for various values of flow rate and magnitude of the imposed magnetic field. The main contributions to the total pressure drop in the test-section have been identified as a function of characteristic flow parameters. For sufficiently strong magnetic fields the non-dimensional pressure losses are practically independent on the flow rate, namely inertia forces become negligible. Previous experiments on MHD flows in a simplified test-section for a HCLL blanket showed that the main contributions to the total pressure drop in a blanket module originate from the flow in the distributing and collecting manifolds. The new experiments confirm that the largest pressure drops occur along manifolds and near the first wall of the blanket module, where the liquid metal passes through small openings in the stiffening plates separating two breeder units. Moreover, the experimental data shows that with the present manifold design the flow does not distribute homogeneously among the 8 stacked boxes that form the breeding zone.

Measurements of impurity concentrations and transport in the Lithium Tokamak Experiment

NASA Astrophysics Data System (ADS)

Boyle, Dennis Patrick

This thesis presents new measurements of core impurity concentrations and transport in plasmas with lithium coatings on all-metal plasma facing components (PFCs) in the Lithium Tokamak Experiment (LTX). LTX is a modest-sized spherical tokamak uniquely capable of operating with large area solid and/or liquid lithium coatings essentially surrounding the entire plasma (as opposed to just the divertor or limiter region in other devices). Lithium (Li) wall-coatings have improved plasma performance and confinement in several tokamaks with carbon (C) PFCs, including the National Spherical Torus Experiment (NSTX). In NSTX, contamination of the core plasma with Li impurities was very low (<0.1%) despite extensive divertor coatings. Low Li levels in NSTX were found to be largely due to neoclassical forces from the high level of C impurities. Studying impurity levels and transport with Li coatings on stainless steel surfaces in LTX is relevant to future devices (including future enhancements to NSTX-Upgrade) with all-metal PFCs. The new measurements in this thesis were enabled by a refurbished Thomson scattering system and improved impurity spectroscopy, primarily using a novel visible spectrometer monitoring several Li, C, and oxygen (O) emission lines. A simple model was used to account for impurities in unmeasured charge states, assuming constant density in the plasma core and constant concentration in the edge. In discharges with solid Li coatings, volume averaged impurity concentrations were low but non-negligible, with 2-4% Li, 0.6-2% C, 0.4-0.7% O, and Z eff<1.2. Transport was assessed using the TRANSP, NCLASS, and MIST codes. Collisions with the main H ions dominated the neoclassical impurity transport, unlike in NSTX, where collisions with C dominated. Furthermore, neoclassical transport coefficients calculated with NCLASS were similar across all impurity species and differed no more than a factor of two, in contrast to NSTX where they differed by an order of magnitude. However, time-independent simulations with MIST indicated that unlike NSTX, neoclassical theory did not fully capture the impurity transport and anomalous transport likely played a significant role in determining impurity profiles.

Measurements of impurity concentrations and transport in the Lithium Tokamak Experiment

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

Boyle, Dennis Patrick

This thesis presents new measurements of core impurity concentrations and transport in plasmas with lithium coatings on all-metal plasma facing components (PFCs) in the Lithium Tokamak Experiment (LTX). LTX is a modest-sized spherical tokamak uniquely capable of operating with large area solid and/or liquid lithium coatings essentially surrounding the entire plasma (as opposed to just the divertor or limiter region in other devices). Lithium (Li) wall-coatings have improved plasma performance and confinement in several tokamaks with carbon (C) PFCs, including the National Spherical Torus Experiment (NSTX). In NSTX, contamination of the core plasma with Li impurities was very low (<0.1%)more » despite extensive divertor coatings. Low Li levels in NSTX were found to be largely due to neoclassical forces from the high level of C impurities. Studying impurity levels and transport with Li coatings on stainless steel surfaces in LTX is relevant to future devices (including future enhancements to NSTX-Upgrade) with all-metal PFCs. The new measurements in this thesis were enabled by a refurbished Thomson scattering system and improved impurity spectroscopy, primarily using a novel visible spectrometer monitoring several Li, C, and oxygen (O) emission lines. A simple model was used to account for impurities in unmeasured charge states, assuming constant density in the plasma core and constant concentration in the edge. In discharges with solid Li coatings, volume averaged impurity concentrations were low but non-negligible, with~2-4% Li, ~0.6-2% C, ~0.4-0.7% O, and Z_eff<1.2. Transport was assessed using the TRANSP, NCLASS, and MIST codes. Collisions with the main H ions dominated the neoclassical impurity transport, unlike in NSTX, where collisions with C dominated. Furthermore, neoclassical transport coefficients calculated with NCLASS were similar across all impurity species and differed no more than a factor of two, in contrast to NSTX where they differed by an order of magnitude. However, time-independent simulations with MIST indicated that unlike NSTX, neoclassical theory did not fully capture the impurity transport and anomalous transport likely played a significant role in determining impurity profiles.« less

Electrospun Nanofiber-Coated Membrane Separators for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Lee, Hun

Lithium-ion batteries are widely used as a power source for portable electronic devices and hybrid electric vehicles due to their excellent energy and power densities, long cycle life, and enhanced safety. A separator is considered to be the critical component in lithium-ion rechargeable batteries. The separator is placed between the positive and negative electrodes in order to prevent the physical contact of electrodes while allowing the transportation of ions. In most commercial lithium-ion batteries, polyolefin microporous membranes are commonly used as the separator due to their good chemical stability and high mechanical strength. However, some of their intrinsic natures, such as low electrolyte uptake, poor adhesion property to the electrodes, and low ionic conductivity, can still be improved to achieve higher performance of lithium-ion batteries. In order to improve these intrinsic properties, polyolefin microporous membranes can be coated with nanofibers by using electrospinning technique. Electrospinning is a simple and efficient method to prepare nanofibers which can absorb a significant amount of liquid electrolyte to achieve low internal resistance and battery performance. This research presents the preparation and investigation of composite membrane separators prepared by coating nanofibers onto polyolefin microporous membranes via electrospinning technique. Polyvinylidene fluoride polymers and copolymers were used for the preparation of electrospun nanofiber coatings because they have excellent electrochemical stability, good adhesion property, and high temperature resistance. The nanofiber coatings prepared by electrospinning form an interconnected and randomly orientated structure on the surface of the polyolefin microporous membranes. The size of the nanofibers is on a scale that does not interfere with the micropores in the membrane substrates. The resultant nanofiber-coated membranes have the potential to combine advantages of both the polyolefin separator membranes and the nanoscale fibrous polymer coatings. The polyolefin microporous membranes serve as the supporting substrate which provides the required mechanical strength for the assembling process of lithium-ion batteries. The electrospun nanofiber coatings improve the wettability of the composite membrane separators to the liquid electrolyte, which is desirable for the lithium-ion batteries with high kinetics and good cycling performance. The results show that the nanofiber-coated membranes have enhanced adhesion properties to the battery electrode which can help prevent the formation of undesirable gaps between the separators and electrodes during prolonged charge-discharge cycles, especially in large-format batteries. The improvement on adhesive properties of nanofiber-coated membranes was evaluated by peel test. Nanofiber coatings applied to polyolefin membrane substrates improve the adhesion of separator membranes to battery electrodes. Electrolyte uptakes, ionic conductivities and interfacial resistances of the nanofiber-coated membrane separators were studied by soaking the membrane separators with a liquid electrolyte solution of 1 M lithium hexafluorophosphate dissolved in ethylene carbonate/dimethylcarbonate/ethylmethyl carbonate (1:1:1 vol). The nanofiber coatings on the surface of the membrane substrates increase the electrolyte uptake capacity due to the high surface area and capillary effect of nanofibers. The nanofiber-coated membranes soaked in the liquid electrolyte solution exhibit high ionic conductivities and low interfacial resistances to the lithium electrode. The cells containing LiFePO 4 cathode and the nanofiber-coated membranes as the separator show high discharge specific capacities and good cycling stability at room temperature. The nanofiber coatings on the membrane substrates contribute to high ionic conductivity and good electrochemical performance in lithium-ion batteries. Therefore, these nanofiber-coated composite membranes can be directly used as novel battery separators for high performance of lithium-ion batteries. Coating polyolefin microporous membranes with electrospun nanofibers is a promising approach to obtain highperformance separators for advanced lithium-ion batteries.

Synthesis and Compatibility of Ionic Liquid Containing Rod-Coil Polyimide Gel Electrolytes with Lithium Metal Electrodes

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Palker, Allyson E.; Meador, Mary Ann B.; Bennett, William R.

2008-01-01

A highly cross-linked polyimide-polyethylene oxide copolymer has been synthesized that is capable of holding large volumes of liquid component, simultaneously maintaining good dimensional stability. An amine end capped oligomer was made that was imidized in solution, followed by reaction with a triisocyanate in the presence of desired additives at ambient temperature. Polymer films are able to hold over 4 times their weight in room temperature ionic liquid RTIL or carbonate solvent. Electrolytes were studied that contained varying amounts of RTIL, lithium trifluoromethanesulfonimide LiTFSi, and alumina nanoparticles. Electrochemical stability of these electrolytes with lithium metal electrodes was studied by galvanic cycling and impedance spectroscopy. Improved cycling stability and decreased interfacial resistance were observed when increasing amounts of RTIL and LiTFSi were added. The addition of small amounts of alumina further decreased interfacial resistance by nearly an order of magnitude. During the course of the study, cycling stability increased from less than 3 to greater than 1000 h at 60 C and 0.25 mA/cm2 current density.

Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy

DOE PAGES

Leenheer, Andrew Jay; Jungjohann, Katherine Leigh; Zavadil, Kevin Robert; ...

2015-03-18

Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm 2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. Themore » effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. As a result, we discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.« less

Ionic liquids in lithium battery electrolytes: Composition versus safety and physical properties

NASA Astrophysics Data System (ADS)

Wilken, Susanne; Xiong, Shizhao; Scheers, Johan; Jacobsson, Per; Johansson, Patrik

2015-02-01

Ionic liquids have been highlighted as non-flammable, environmentally friendly, and suggested as possible solvents in lithium ion battery electrolytes. Here, the application of two ionic liquids from the EMIm-family in a state-of-the-art carbonate solvent based electrolyte is studied with a focus on safety improvement. The impact of the composition on physical and safety related properties is investigated for IL concentrations of additive (∼5 wt%) up to co-solvent concentrations (∼60 wt%). Furthermore, the role of the lithium salt concentration is separately addressed by studying a set of electrolytes at 0.5 M, 1 M, and 2 M LiPF6 concentrations. A large impact on the electrolyte properties is found for the electrolytes containing EMImTFSI and high salt concentrations. The composition 2 M LiPF6 EC:DEC:IL (1:1:3 wt%) is found non-flammable for both choices of ILs added. The macroscopic observations are complemented by a Raman spectroscopy analysis whereby a change in the Li+ solvation is detected for IL concentrations >4.5 mol%.

A lithium superionic conductor.

PubMed

Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, Akio

2011-07-31

Batteries are a key technology in modern society. They are used to power electric and hybrid electric vehicles and to store wind and solar energy in smart grids. Electrochemical devices with high energy and power densities can currently be powered only by batteries with organic liquid electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems very complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10(-2) S cm(-1)) only at 50-80 °C, which is one order of magnitude lower than those of organic liquid electrolytes. Here, we report a lithium superionic conductor, Li(10)GeP(2)S(12) that has a new three-dimensional framework structure. It exhibits an extremely high lithium ionic conductivity of 12 mS cm(-1) at room temperature. This represents the highest conductivity achieved in a solid electrolyte, exceeding even those of liquid organic electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochemical properties (high conductivity and wide potential window).

Helium retention and Hydrogen absorption in FLiRE

NASA Astrophysics Data System (ADS)

Schultz, Benjamin

2005-10-01

The FLiRE (Flowing Lithium Retention Experiment) facility consists of a flow loop which contains a two sections to observe flow along ramps in an upper chamber. As the Li exits the upper chamber it makes a vacuum seal isolation of the upper chamber from a lower one where thermal desporption spectroscopy can take place. By applying an ion beam or a plasma pulse to the open-channel Li flow on the ramp, studies can be made of He and H retention by measuring the partial pressure of He in the lower TDS chamber. Previous studies have shown about a 1% to 2% retention of He over a time scale sufficient to exit a potential flowing Li-walled reactor. The significance of such a result is very high and needs to be verified. It is possible that He implanted in the ramp before flow was initiated was absorbed leading to the observed increase. The experiment has been altered to address this and other concerns. Research on hydrogen absorption in liquid lithium exposed to hydrogen plasma has also been conducted. Overall results and their implications towards large scale fusion reactors are given.

Nano-sponge ionic liquid-polymer composite electrolytes for solid-state lithium power sources

NASA Astrophysics Data System (ADS)

Liao, Kang-Shyang; Sutto, Thomas E.; Andreoli, Enrico; Ajayan, Pulickel; McGrady, Karen A.; Curran, Seamus A.

Solid polymer gel electrolytes composed of 75 wt.% of the ionic liquid, 1- n-butyl-2,3-dimethylimidazolium bis-trifluoromethanesulfonylimide with 1.0 M lithium bis-trifluoromethanesulfonylimide and 25 wt.% poly(vinylidenedifluoro-hexafluoropropene) are characterized as the electrolyte/separator in solid-state lithium batteries. The ionic conductivity of these gels ranges from 1.5 to 2.0 mS cm -1, which is several orders of magnitude more conductive than any of the more commonly used solid polymers, and comparable to the best solid gel electrolytes currently used in industry. TGA indicates that these polymer gel electrolytes are thermally stable to over 280 °C, and do not begin to thermally decompose until over 300 °C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these thin film batteries, 150 charge-discharge cycles are run for Li xCoO 2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects are observed over the charging cycles, indicating the high ionic conductivity of the ionic liquid solid polymer gel electrolyte. The overall cell efficiency is approximately 98%, and no significant loss in battery efficiency is observed over the 150 cycles.

Understanding transport mechanisms in ionic liquid/carbonate solvent electrolyte blends.

PubMed

Oldiges, K; Diddens, D; Ebrahiminia, M; Hooper, J B; Cekic-Laskovic, I; Heuer, A; Bedrov, D; Winter, M; Brunklaus, G

2018-06-20

To unravel mechanistic details of the ion transport in liquid electrolytes, blends of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI), ethylene carbonate (EC) and dimethyl carbonate (DMC) with the conducting salts lithium hexafluorophosphate (LiPF6) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) were investigated as a function of the IL concentration. Electrochemical impedance, Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR) and Raman spectroscopy supported by Molecular Dynamics (MD) simulations allowed the structural and dynamic correlations of the ion motions to be probed. Remarkably, we identified that though the individual correlations among different ion types exhibit a clear concentration dependence, their net effect is nearly constant throughout the entire concentration range, resulting in approximately equal transport and transference numbers, despite a monitored cross-over from carbonate-based lithium coordination to a TFSI-based ion coordination. In addition, though dynamical ion correlation could be found, the absolute values of the ionic conductivity are essentially determined by the overall viscosity of the electrolyte. The IL/carbonate blends with a Pyr14TFSI fraction of ∼10 wt% are found to be promising electrolyte solvents, with ionic conductivities and lithium ion transference numbers comparable to those of standard carbonate-based electrolytes while the thermal and electrochemical stabilities are considerably improved. In contrast, the choice of the conducting salt only marginally affects the transport properties.

Contributions to the Data on Theoretical Metallurgy. 3. The Free Energies of Vaporization and Vapor Pressures of Inorganic Substances

DTIC Science & Technology

1935-01-01

109ead-------------59 Vapor-pressure table ----------- 110 Lithium -------------------- 63 Bibliography ----------------- 115 Acceson orj NYTIS CRAMI ti...852-926*) have measured the vapor pressure of lithium in the liquid state, and Ruff and Jobannsen (32~4) have stated that the boili point is above...the results of th~e three investigations on ii u{id lithium do not agree, some arbitrar choice must be made. V this case, the data of Hartmann and

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.

Gas production apparatus

DOEpatents

Winsche, Warren E.; Miles, Francis T.; Powell, James R.

1976-01-01

This invention relates generally to the production of gases, and more particularly to the production of tritium gas in a reliable long operating lifetime systems that employs solid lithium to overcome the heretofore known problems of material compatibility and corrosion, etc., with liquid metals. The solid lithium is irradiated by neutrons inside low activity means containing a positive (+) pressure gas stream for removing and separating the tritium from the solid lithium, and these means are contained in a low activity shell containing a thermal insulator and a neutron moderator.

Towards quantification of toxicity of lithium ion battery electrolytes - development and validation of a liquid-liquid extraction GC-MS method for the determination of organic carbonates in cell culture materials.

PubMed

Strehlau, Jenny; Weber, Till; Lürenbaum, Constantin; Bornhorst, Julia; Galla, Hans-Joachim; Schwerdtle, Tanja; Winter, Martin; Nowak, Sascha

2017-10-01

A novel method based on liquid-liquid extraction with subsequent gas chromatography separation and mass spectrometric detection (GC-MS) for the quantification of organic carbonates in cell culture materials is presented. Method parameters including the choice of extraction solvent, of extraction method and of extraction time were optimised and the method was validated. The setup allowed for determination within a linear range of more than two orders of magnitude. The limits of detection (LODs) were between 0.0002 and 0.002 mmol/L and the repeatability precisions were in the range of 1.5-12.9%. It could be shown that no matrix effects were present and recovery rates between 98 and 104% were achieved. The methodology was applied to cell culture models incubated with commercial lithium ion battery (LIB) electrolytes to gain more insight into the potential toxic effects of these compounds. The stability of the organic carbonates in cell culture medium after incubation was studied. In a porcine model of the blood-cerebrospinal fluid (CSF) barrier, it could be shown that a transfer of organic carbonates into the brain facing compartment took place. Graphical abstract Schematic setup for the investigation of toxicity of lithium ion battery electrolytes.

Superior Conductive Solid-like Electrolytes: Nanoconfining Liquids within the Hollow Structures

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

Zhang, Jinshui; Bai, Ying; Sun, Xiao-Guang

2015-01-01

The growth and proliferation of lithium (Li) dendrites during cell recharge is unavoidable, which seriously hinders the development and application of rechargeable Li metal batteries. Solid electrolytes with robust mechanical modulus are regarded as a promising approach to overcome the dendrite problems. However, their room-temperature ionic conductivities are usually too low to reach the level required for normal battery operation. Here, a class of novel solid electrolytes with liquid-like room-temperature ionic conductivities (> 1 mS cm-1) has been successfully synthesized by taking advantage of the unique nanoarchitectures of hollow silica (HS) spheres to confine liquid electrolytes in hollow space tomore » afford high conductivities. In a symmetric lithium/lithium cell, such kind of solid-like electrolytes demonstrates a robust performance against Li dendrite problems, well stabilizing the cell system from short circuiting in a long-time operation at current densities ranging from 0.16 to 0.32 mA cm-2. Moreover, the high flexibility and compatibility of HS nanoarchitectures, in principle, enables broad tunability to choose desired liquids for the fabrication of other kinds of solid-like electrolytes, such as those containing Na+, Mg2+ or Al3+ as conductive media, providing a useful alternative strategy for the development of next generation rechargeable batteries.« less

Hydrodynamic and shock heating instabilities of liquid metal strippers for RIA

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

Hassanein, Ahmed

2013-05-24

Stripping of accelerated ions is a key problem for the design of RIA to obtain high efficiency. Thin liquid Lithium film flow is currently considered as stripper for RIA ion beams to obtain higher Z for following acceleration: in extreme case of Uranium from Z=29 to Z=60-70 (first stripper) and from Z=70 till full stripping Z=92 (second stripper). Ionization of ion occurs due to the interaction of the ion with electrons of target material (Lithium) with the loss of parts of the energy due to ionization, Q{sub U}, which is also accompanied with ionization energy losses, Q{sub Li} of themore » lithium. The resulting heat is so high that can be removed not by heat conduction but mainly by convection, i.e., flowing of liquid metal across beam spot area. The interaction of the beam with the liquid metal generates shock wave propagating along direction perpendicular to the beam as well as excites oscillations along beam direction. We studied the dynamics of these excited waves to determine conditions for film stability at the required velocities for heat removal. It will allow optimizing jet nozzle shapes and flow parameters to prevent film fragmentation and to ensure stable device operation.« less

New Liquid Cathodes for Lithium Batteries. Part A. Halocarbons,

DTIC Science & Technology

1984-05-01

difluoroethane , 99 percent; PCR Inc. thionyl chloride, doubly-distilled, Apache Chemicals, Seward, Ill. l.5M LiAlCI4 in SOC1 2 , ɝppm Fe, Lithium Corp. of...tetrachloroethane, and 1,2-dichloro-l,1- difluoroethane appeared stable towards Li during the study. When in contact with electrolyte solutions of 50

Reliability and Maintainability Data for Lead Lithium Cooling Systems

DOE PAGES

Cadwallader, Lee

2016-11-16

This article presents component failure rate data for use in assessment of lead lithium cooling systems. Best estimate data applicable to this liquid metal coolant is presented. Repair times for similar components are also referenced in this work. These data support probabilistic safety assessment and reliability, availability, maintainability and inspectability analyses.

Additive-containing ionic liquid electrolytes for secondary lithium battery

NASA Astrophysics Data System (ADS)

Xu, Jinqiang; Yang, Jun; NuLi, Yanna; Wang, Jiulin; Zhang, Zongshuang

Room temperature ionic liquid (RTIL) consisting of N-methyl- N-propylpiperidinium (PP13) cation and bis(trifluoromethanesulfonyl)imide (TFSI) anion was synthesized and its electrochemical stability was investigated in comparison with 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF 4) and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF 6). The electrochemical window of PP13-TFSI (5.8 V versus Li/Li +) is wider than that of BMIBF 4 (4.7 V) and BMIPF 6 (4.5 V). The cathodic limit of the PP13-TFSI is about -0.3 V versus Li/Li +, against 0.7 V for BMIPF 6 and BMIBF 4, so it may be used as the electrolyte for second lithium batteries based on lithium anode. In this work, charge efficiency of lithium plating/striping on nickel substrate and the cycle life have been measured using 0.4 M LiTFSI/PP13-TFSI electrolyte both without and with additives such as vinyl acetate (VA), ethylene sulfite (ES), and ethylene carbonate (EC). Remarkable improvement in cycling efficiency and cycle life was found for EC as additive.

Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

NASA Astrophysics Data System (ADS)

Li, Qin; Ardebili, Haleh

2016-01-01

The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

Ceramic and polymeric solid electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

Lithium-ion batteries are important for energy storage in a wide variety of applications including consumer electronics, transportation and large-scale energy production. The performance of lithium-ion batteries depends on the materials used. One critical component is the electrolyte, which is the focus of this paper. In particular, inorganic ceramic and organic polymer solid-electrolyte materials are reviewed. Solid electrolytes provide advantages in terms of simplicity of design and operational safety, but typically have conductivities that are lower than those of organic liquid electrolytes. This paper provides a comparison of the conductivities of solid-electrolyte materials being used or developed for use in lithium-ion batteries.

Technical Challenges for Vehicle 14V/28V Lithium Ion Battery Replacement

DTIC Science & Technology

2011-01-19

or lithium iron phosphate ( LiFePO4 ), on a current collector of aluminum foil, (iii) a microporous separator between the electrodes, and (iv) a liquid...with four LiFePO4 lithium ion cells will likely result in a closely matched voltage. However, other types of lithium ion cells also consisting of...20.5 15- 24.6 17.5- 28.7 20- 32.8 22.5- 36.9 Voltage(V) ( LiFePO4 ) 3.3 6.6 9.9 13.2 16.5 19.8 23.1 26.4 29.7 n x 3.3 Voltage range (V

Lithium levels in tap water and psychotic experiences in a general population of adolescents.

PubMed

Shimodera, Shinji; Koike, Shinsuke; Ando, Shuntaro; Yamasaki, Syudo; Fujito, Ryosuke; Endo, Kaori; Iijima, Yudai; Yamamoto, Yu; Morita, Masaya; Sawada, Ken; Ohara, Nobuki; Okazaki, Yuji; Nishida, Atsushi

2018-06-09

Recently, several epidemiologic studies have reported that lithium in drinking water may be associated with lower rates of suicide mortality, lower incidence of dementia, and lower levels of adolescents' depression and aggression at the population level. However, to our knowledge, no study has investigated lithium level in tap water in relation to psychotic experiences in a general population of adolescents. This is the first study to investigate this using a large dataset. Information on psychotic experiences, distress associated with these experiences, and depressive symptoms were collected in 24 public junior high schools in Kochi Prefecture in Japan. Samples were collected from sources that supplied drinking water to schools, and lithium levels were measured using atomic absorption spectrophotometry. The association of lithium levels with psychotic experiences, considering distress as a degree of severity, was examined using an ordinal logistic regression model with schools and depressive symptoms as random effects. In total, 3040 students responded to the self-reporting questionnaire (response rate: 91.8%). Lithium levels in tap water were inversely associated with psychotic experiences (p = 0.021). We concluded that lithium level in tap water was inversely associated with psychotic experiences among a general population of adolescents and may have a preventive effect for such experiences and distress. Copyright © 2018 Elsevier B.V. All rights reserved.

Lithium bis(fluorosulfonyl)imide (LiFSI) as conducting salt for nonaqueous liquid electrolytes for lithium-ion batteries: Physicochemical and electrochemical properties

NASA Astrophysics Data System (ADS)

Han, Hong-Bo; Zhou, Si-Si; Zhang, Dai-Jun; Feng, Shao-Wei; Li, Li-Fei; Liu, Kai; Feng, Wen-Fang; Nie, Jin; Li, Hong; Huang, Xue-Jie; Armand, Michel; Zhou, Zhi-Bin

Lithium bis(fluorosulfonyl)imide (LiFSI) has been studied as conducting salt for lithium-ion batteries, in terms of the physicochemical and electrochemical properties of the neat LiFSI salt and its nonaqueous liquid electrolytes. Our pure LiFSI salt shows a melting point at 145 °C, and is thermally stable up to 200 °C. It exhibits far superior stability towards hydrolysis than LiPF 6. Among the various lithium salts studied at the concentration of 1.0 M (= mol dm -3) in a mixture of ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (3:7, v/v), LiFSI shows the highest conductivity in the order of LiFSI > LiPF 6 > Li[N(SO 2CF 3) 2] (LiTFSI) > LiClO 4 > LiBF 4. The stability of Al in the high potential region (3.0-5.0 V vs. Li +/Li) has been confirmed for high purity LiFSI-based electrolytes using cyclic voltammetry, SEM morphology, and chronoamperometry, whereas Al corrosion indeed occurs in the LiFSI-based electrolytes tainted with trace amounts of LiCl (50 ppm). With high purity, LiFSI outperforms LiPF 6 in both Li/LiCoO 2 and graphite/LiCoO 2 cells.

Mechanism of Formation of Li 7 P 3 S 11 Solid Electrolytes through Liquid Phase Synthesis

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

Wang, Yuxing; Lu, Dongping; Bowden, Mark

Crystalline Li7P3S11 is a promising solid electrolyte for all solid state lithium/lithium ion batteries. A controllable liquid phase synthesis of Li7P3S11 is more desirable compared to conventional mechanochemical synthesis, but recent attempts suffer from reduced ionic conductivities. Here we elucidate the formation mechanism of crystalline Li7P3S11 synthesized in the liquid phase (acetonitrile, or ACN). We conclude that the crystalline Li7P3S11 forms through a two-step reaction: 1) formation of solid Li3PS4∙ACN and amorphous Li2S∙P2S5 phases in the liquid phase; 2) solid-state conversion of the two phases. The implication of this two-step reaction mechanism to the morphology control and the transport propertiesmore » of liquid phase synthesized Li7P3S11 is identified and discussed.« less

Test facility for investigation of heat transfer of promising coolants for the nuclear power industry

NASA Astrophysics Data System (ADS)

Belyaev, I. A.; Sviridov, V. G.; Batenin, V. M.; Biryukov, D. A.; Nikitina, I. S.; Manchkha, S. P.; Pyatnitskaya, N. Yu.; Razuvanov, N. G.; Sviridov, E. V.

2017-11-01

The results are presented of experimental investigations into liquid metal heat transfer performed by the joint research group consisting of specialist in heat transfer and hydrodynamics from NIU MPEI and JIHT RAS. The program of experiments has been prepared considering the concept of development of the nuclear power industry in Russia. This concept calls for, in addition to extensive application of water-cooled, water-moderated (VVER-type) power reactors and BN-type sodium cooled fast reactors, development of the new generation of BREST-type reactors, fusion power reactors, and thermonuclear neutron sources. The basic coolants for these nuclear power installations will be heavy liquid metals, such as lead and lithium-lead alloy. The team of specialists from NRU MPEI and JIHT RAS commissioned a new RK-3 mercury MHD-test facility. The major components of this test facility are a unique electrical magnet constructed at Budker Nuclear Physics Institute and a pressurized liquid metal circuit. The test facility is designed for investigating upward and downward liquid metal flows in channels of various cross-sections in a transverse magnetic field. A probe procedure will be used for experimental investigation into heat transfer and hydrodynamics as well as for measuring temperature, velocity, and flow parameter fluctuations. It is generally adopted that liquid metals are the best coolants for the Tokamak reactors. However, alternative coolants should be sought for. As an alternative to liquid metal coolants, molten salts, such as fluorides of lithium and beryllium (so-called FLiBes) or fluorides of alkali metals (so-called FLiNaK) doped with uranium fluoride, can be used. That is why the team of specialists from NRU MPEI and JIHT RAS, in parallel with development of a mercury MHD test facility, is designing a test facility for simulating molten salt heat transfer and hydrodynamics. Since development of this test facility requires numerical predictions and verification of numerical codes, all examined configurations of the MHD flow are also investigated numerically.

Analysis of a hydrometallurgical route to recover base metals from spent rechargeable batteries by liquid-liquid extraction with Cyanex 272

NASA Astrophysics Data System (ADS)

Mantuano, Danuza Pereira; Dorella, Germano; Elias, Renata Cristina Alves; Mansur, Marcelo Borges

A hydrometallurgical route is proposed to recover zinc and manganese from spent alkaline batteries in order to separate base metals such as nickel, copper, aluminium, cadmium, lithium and cobalt which constitute the main metallic species of spent NiCd, NiMH and Li-ion rechargeable batteries. The route comprises the following main steps: (1) sorting batteries by type, (2) battery dismantling to separate the spent battery dust from plastic, iron scrap and paper, (3) leaching of the dust with sulphuric acid and (4) metal separation by a liquid-liquid extraction using Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) as extractant. The metal content of NiCd, NiMH and Li-ion batteries from three distinct manufacturers has been evaluated. A factorial design of experiments was used to investigate the leaching step using operational variables such as temperature, H 2SO 4 concentration, S/L ratio and H 2O 2 concentration. Analysis of metal separation by the liquid-liquid extraction with Cyanex 272 identified a pH 1/2 2.5-3.0 for zinc and aluminium, pH 1/2 4.0-4.5 for manganese, cadmium, copper and cobalt, pH 1/2 6.5 for nickel and pH 1/2 8.0 for lithium. These results indicate that batteries must be previously sorted by type and treated separately. In addition, data fitting to an equilibrium model proposed for the reactive test system by the European Federation of Chemical Engineering (EFChE) have indicated that MR 2(RH) 2 and MR 2 complexes (where M = Zn, Mn, Co, Cd and Cu) co-exist in the organic phase with Cyanex 272 depending on the loading conditions. The route has been found technically viable to separate the main metallic species of all batteries considered in this study.

Nonflammable gel electrolyte containing alkyl phosphate for rechargeable lithium batteries

NASA Astrophysics Data System (ADS)

Yoshimoto, Nobuko; Niida, Yoshihiro; Egashira, Minato; Morita, Masayuki

A nonflammable polymeric gel electrolyte has been developed for rechargeable lithium battery systems. The gel film consists of poly(vinylidenefluoride- co-hexafluoropropylene) (PVdF-HFP) swollen with lithium hexafluorophosphate (LiPF 6) solution in ternary solvent containing trimethyl phosphate (TMP). High ionic conductivity of 6.2 mS cm -1 at 20 °C was obtained for the gel electrolyte consisting of 0.8 M LiPF 6/EC + DEC + TMP (55:25:20) with PVdF-HFP, which is comparable to that of the liquid electrolyte containing the same electrolytic salt. Addition of a small amount of vinylene carbonate (VC) in the gel electrolyte improved the rechargeability of a graphite electrode. The rechargeable capacity of the graphite in the gel containing VC was ca. 300 mAh g -1, which is almost the same as that in a conventional liquid electrolyte system.

Thermally-responsive, nonflammable phosphonium ionic liquid electrolytes for lithium metal batteries: operating at 100 degrees celsius.

PubMed

Lin, X; Kavian, R; Lu, Y; Hu, Q; Shao-Horn, Y; Grinstaff, M W

2015-11-13

Rechargeable batteries such as Li ion/Li metal batteries are widely used in the electronics market but the chemical instability of the electrolyte limits their use in more demanding environmental conditions such as in automotive, oil exploration, or mining applications. In this study, a series of alkyl phosphonium ionic liquid electrolyte are described with high thermal stability and solubility for LiTFSI. A lithium metal battery (LMB) containing a tailored phosphonium ionic liquid/LiTFSI electrolyte operates at 100 °C with good specific capacities and cycling stability. Substantial capacity is maintained during 70 cycles or 30 days. Instant on-off battery operation is realized via the significant temperature dependence of the electrolyte material, demonstrating the robustness and potential for use at high temperature.

Enhanced low-temperature lithium storage performance of multilayer graphene made through an improved ionic liquid-assisted synthesis

NASA Astrophysics Data System (ADS)

Raccichini, Rinaldo; Varzi, Alberto; Chakravadhanula, Venkata Sai Kiran; Kübel, Christian; Balducci, Andrea; Passerini, Stefano

2015-05-01

The electrochemical properties of graphene are strongly depending on its synthesis. Between the different methods proposed so far, liquid phase exfoliation turns out to be a promising method for the production of graphene. Unfortunately, the low yield of this technique, in term of solid material obtained, still limit its use to small scale applications. In this article we propose a low cost and environmentally friendly method for producing multilayer crystalline graphene with high yield. Such innovative approach, involving an improved ionic liquid assisted, microwave exfoliation of expanded graphite, allows the production of graphene with advanced lithium ion storage performance, for the first time, at low temperatures (<0 °C), as low as -30 °C, with respect to commercially available graphite.

All Solid State Rechargeable Lithium Batteries using Block Copolymers

NASA Astrophysics Data System (ADS)

Hallinan, Daniel; Balsara, Nitash

2011-03-01

The growing need for alternative energy and increased demand for mobile technology require higher density energy storage. Existing battery technologies, such as lithium ion, are limited by theoretical energy density as well as safety issues. Other battery chemistries are promising options for dramatically increasing energy density. Safety can be improved by replacing the flammable, reactive liquids used in existing lithium-ion battery electrolytes with polymer electrolytes. Block copolymers are uniquely suited for this task because ionic conductivity and mechanical strength, both important properties in battery formulation, can be independently controlled. In this study, lithium batteries were assembled using lithium metal as negative electrode, polystyrene-b-poly(ethylene oxide) copolymer with lithium salt as electrolyte, and a positive electrode. The positive electrode consisted of polymer electrolyte for ion conduction, carbon for electron conduction, and an active material. Batteries were charged and discharged over many cycles. The battery cycling results were compared to a conventional battery chemistry.

Selection of new Kynar-based electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Christie, Alasdair M.; Christie, Lynn; Vincent, Colin A.

New electrolyte solution compositions have been identified for use in lithium-ion batteries after gelling with an appropriate quantity of Kynar polymer. Since the Li + conducting medium is largely the liquid electrolyte component, the assessment of these solutions as suitable lithium-ion cell candidates were investigated before adding the polymer. Selected electrolyte solutions were then used in the preparation of polymer gels. The specific conductivities of Kynar-based gels were determined as a function of salt concentration and polymer concentration. Optimised self-supporting polymer films, based on mixtures of ethylene carbonate (EC), ethylmethyl carbonate (EMC) and lithium hexafluorophosphate (LiPF 6) or lithium tetrafluoroborate (LiBF 4), showed good high current density cycling performance when used as separators in coke and Li 1- xMn 2O 4 (spinel) half-cells.

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.

Hydraulic Actuator for Ganged Control Rods

NASA Technical Reports Server (NTRS)

Thompson, D. C.; Robey, R. M.

1986-01-01

Hydraulic actuator moves several nuclear-reactor control rods in unison. Electromagnetic pump pushes liquid lithium against ends of control rods, forcing them out of or into nuclear reactor. Color arrows show lithium flow for reactor startup and operation. Flow reversed for shutdown. Conceived for use aboard spacecraft, actuator principle applied to terrestrial hydraulic machinery involving motion of ganged rods.

Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

NASA Astrophysics Data System (ADS)

Kartini, Evvy; Manawan, Maykel

2016-02-01

With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say "the most important emerging energy technology" is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner's cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes, promise the potential to replace organic liquid electrolytes and thereby improve the safety of next-generation high-energy batteries. Li3PO4 has been proved to be a good candidate for solid electrolyte, due to its easy in preparation, low cost, high melting temperature and good compatibility with the electrode materials. In the present work, Li3PO4 has been prepared by wet chemical reaction, a simple method with the advantage of recycling a waste product H3PO4. The crystal structure has been characterized by both neutron and x-ray diffraction. The use of neutron scattering plays important role on observing the light atoms such as lithium ion. The x-ray diffraction results showed the crystal structure of orthorhombic phase P m n 21 (31), that belongs to the β-Li3PO4, with the lattice parameters are a = 6.123872, b = 5.250211, c = 4.876378. The conductivity of β-Li3PO4 was around 10-8 S/cm. Furthermore, the future application of the solid electrolyte layer in lithium ion battery will also be considered. It is concluded that the used of local resources on producing the solid electrolyte Li3PO4 for lithium ion battery will give more added values to the researches and national industry.

Liquid lithium loop system to solve challenging technology issues for fusion power plant

DOE PAGES

Ono, Masayuki; Majeski, Richard P.; Jaworski, Michael A.; ...

2017-07-12

Here, steady-state fusion power plant designs present major divertor technology challenges, including high divertor heat flux both in steady-state and during transients. In addition to these concerns, there are the unresolved technology issues of long term dust accumulation and associated tritium inventory and safety issues. It has been suggested that radiation-based liquid lithium (LL) divertor concepts with a modest lithium-loop could provide a possible solution for these outstanding fusion reactor technology issues, while potentially improving reactor plasma performance. The application of lithium (Li) in NSTX resulted in improved H-mode confinement, H-mode power threshold reduction, and reduction in the divertor peakmore » heat flux while maintaining essentially Li-free core plasma operation even during H-modes. These promising results in NSTX and related modeling calculations motivated the radiative liquid lithium divertor (RLLD) concept and its variant, the active liquid lithium divertor concept (ARLLD), taking advantage of the enhanced or non-coronal Li radiation in relatively poorly confined divertor plasmas. To maintain the LL purity in a 1 GW-electric class fusion power plant, a closed LL loop system with a modest circulating capacity of ~ 1 liter/second (l/sec) is envisioned. We examined two key technology issues: 1) dust or solid particle removal and 2) real time recovery of tritium from LL while keeping the tritium inventory level to an acceptable level. By running the LL-loop continuously, it can carry the dust particles and impurities generated in the vacuum vessel to the outside where the dust / impurities can be removed by relatively simple dust filter, cold trap and/or centrifugal separation systems. With ~ 1 l/sec LL flow, even a small 0.1% dust content by weight (or 0.5 g per sec) suggests that the LL-loop could carry away nearly 16 tons of dust per year. In a 1 GW-electric (or ~ 3 GW fusion power) fusion power plant, about 0.5 g / sec of tritium is needed to maintain the fusion fuel cycle assuming ~ 1 % fusion burn efficiency. It appears feasible to recover tritium (T) in real time from LL while maintaining an acceptable T inventory level. Laboratory tests are being conducted to investigate T recovery feasibility with the surface cold trap (SCT) concept.« less

Liquid lithium loop system to solve challenging technology issues for fusion power plant

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

Ono, Masayuki; Majeski, Richard P.; Jaworski, Michael A.

Here, steady-state fusion power plant designs present major divertor technology challenges, including high divertor heat flux both in steady-state and during transients. In addition to these concerns, there are the unresolved technology issues of long term dust accumulation and associated tritium inventory and safety issues. It has been suggested that radiation-based liquid lithium (LL) divertor concepts with a modest lithium-loop could provide a possible solution for these outstanding fusion reactor technology issues, while potentially improving reactor plasma performance. The application of lithium (Li) in NSTX resulted in improved H-mode confinement, H-mode power threshold reduction, and reduction in the divertor peakmore » heat flux while maintaining essentially Li-free core plasma operation even during H-modes. These promising results in NSTX and related modeling calculations motivated the radiative liquid lithium divertor (RLLD) concept and its variant, the active liquid lithium divertor concept (ARLLD), taking advantage of the enhanced or non-coronal Li radiation in relatively poorly confined divertor plasmas. To maintain the LL purity in a 1 GW-electric class fusion power plant, a closed LL loop system with a modest circulating capacity of ~ 1 liter/second (l/sec) is envisioned. We examined two key technology issues: 1) dust or solid particle removal and 2) real time recovery of tritium from LL while keeping the tritium inventory level to an acceptable level. By running the LL-loop continuously, it can carry the dust particles and impurities generated in the vacuum vessel to the outside where the dust / impurities can be removed by relatively simple dust filter, cold trap and/or centrifugal separation systems. With ~ 1 l/sec LL flow, even a small 0.1% dust content by weight (or 0.5 g per sec) suggests that the LL-loop could carry away nearly 16 tons of dust per year. In a 1 GW-electric (or ~ 3 GW fusion power) fusion power plant, about 0.5 g / sec of tritium is needed to maintain the fusion fuel cycle assuming ~ 1 % fusion burn efficiency. It appears feasible to recover tritium (T) in real time from LL while maintaining an acceptable T inventory level. Laboratory tests are being conducted to investigate T recovery feasibility with the surface cold trap (SCT) concept.« less

Liquid lithium loop system to solve challenging technology issues for fusion power plant

NASA Astrophysics Data System (ADS)

Ono, M.; Majeski, R.; Jaworski, M. A.; Hirooka, Y.; Kaita, R.; Gray, T. K.; Maingi, R.; Skinner, C. H.; Christenson, M.; Ruzic, D. N.

2017-11-01

Steady-state fusion power plant designs present major divertor technology challenges, including high divertor heat flux both in steady-state and during transients. In addition to these concerns, there are the unresolved technology issues of long term dust accumulation and associated tritium inventory and safety issues. It has been suggested that radiation-based liquid lithium (LL) divertor concepts with a modest lithium-loop could provide a possible solution for these outstanding fusion reactor technology issues, while potentially improving reactor plasma performance. The application of lithium (Li) in NSTX resulted in improved H-mode confinement, H-mode power threshold reduction, and reduction in the divertor peak heat flux while maintaining essentially Li-free core plasma operation even during H-modes. These promising results in NSTX and related modeling calculations motivated the radiative liquid lithium divertor concept and its variant, the active liquid lithium divertor concept, taking advantage of the enhanced or non-coronal Li radiation in relatively poorly confined divertor plasmas. To maintain the LL purity in a 1 GW-electric class fusion power plant, a closed LL loop system with a modest circulating capacity of ~1 l s-1 is envisioned. We examined two key technology issues: (1) dust or solid particle removal and (2) real time recovery of tritium from LL while keeping the tritium inventory level to an acceptable level. By running the LL-loop continuously, it can carry the dust particles and impurities generated in the vacuum vessel to the outside where the dust/impurities can be removed by relatively simple dust filter, cold trap and/or centrifugal separation systems. With ~1 l s-1 LL flow, even a small 0.1% dust content by weight (or 0.5 g s-1) suggests that the LL-loop could carry away nearly 16 tons of dust per year. In a 1 GW-electric (or ~3 GW fusion power) fusion power plant, about 0.5 g s-1 of tritium is needed to maintain the fusion fuel cycle assuming ~1% fusion burn efficiency. It appears feasible to recover tritium (T) in real time from LL while maintaining an acceptable T inventory level. Laboratory tests are being conducted to investigate T recovery feasibility with the surface cold trap concept.

Surface Structure of Liquid Li and Na: An ab initio Molecular Dynamics Study

NASA Astrophysics Data System (ADS)

González, D. J.; González, L. E.; Stott, M. J.

2004-02-01

Molecular dynamics simulations of the liquid-vapor interfaces of liquid metals have been performed using first principles methods. Results are presented for liquid lithium and sodium near their respective triple points, for samples of 2000 particles in a slab geometry. The atomic density profiles show a pronounced stratification extending several atomic diameters into the bulk, which is similar to that already experimentally observed in liquid K, Ga, In, and Hg.

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Experimental study of an air-cooled thermal management system for high capacity lithium-titanate batteries

NASA Astrophysics Data System (ADS)

Giuliano, Michael R.; Prasad, Ajay K.; Advani, Suresh G.

2012-10-01

Lithium-titanate batteries have become an attractive option for battery electric vehicles and hybrid electric vehicles. In order to maintain safe operating temperatures, these batteries must be actively cooled during operation. Liquid-cooled systems typically employed for this purpose are inefficient due to the parasitic power consumed by the on-board chiller unit and the coolant pump. A more efficient option would be to circulate ambient air through the battery bank and directly reject the heat to the ambient. We designed and fabricated such an air-cooled thermal management system employing metal-foam based heat exchanger plates for sufficient heat removal capacity. Experiments were conducted with Altairnano's 50 Ah cells over a range of charge-discharge cycle currents at two air flow rates. It was found that an airflow of 1100 mls-1 per cell restricts the temperature rise of the coolant air to less than 10 °C over ambient even for 200 A charge-discharge cycles. Furthermore, it was shown that the power required to drive the air through the heat exchanger was less than a conventional liquid-cooled thermal management system. The results indicate that air-cooled systems can be an effective and efficient method for the thermal management of automotive battery packs.

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.

An approach to beneficiation of spent lithium-ion batteries for recovery of materials

NASA Astrophysics Data System (ADS)

Marinos, Danai

Lithium ion batteries are one of the most commonly used batteries. A large amount of these have been used over the past 25 years and the use is expected to rise more due to their use in automotive batteries. Lithium ion batteries cannot be disposed into landfill due to safety reasons and cost. Thus, over the last years, there has been a lot of effort to find ways to recycle lithium ion batteries. A lot of valuable materials are present in a lithium ion battery making their recycling favorable. Many attempts, including pyrometallurgical and hydrometallurgical methods, have been researched and some of them are already used by the industry. However, further improvements are needed to the already existing processes, to win more valuable materials, use less energy and be more environmentally benign. The goal of this thesis is to find a low-temperature, low-energy method of recovering lithium from the electrolyte and to develop pathways for complete recycling of the battery. The research consists of the following parts: Pure LiPF6 powder, which is the electrolyte material, was characterized using x- ray diffraction analysis and DSC/TGA analysis. The LiPF6 powder was titrated using acid (HCl, HNO3, H2SO4), bases (NH4 OH) and distilled water. It was concluded that distilled water was the best solvent to selectively leach lithium from lithium-ion batteries. Leaching conditions were optimized including time, temperature, solid/liquid ratio and stirring velocity. All the samples were tested using ICP for chemical composition. Because leaching could be performed at room temperature, leaching was conducted in a flotation machine that was able to separate plastics by creating bubbles with no excess reagents use. The solution that contained lithium had to be concentrated more in order for lithium to be able to precipitate and it was shown that the solution could be concentrated by using the same solution over and over again. The next set of experiments was composed of battery shredding, steel separation by hand magnet, leaching with distilled water and sizing using wet sieving. Every fraction was sent to rare-earth rolls separation and eddy current separation. A size distribution analysis was conducted and the fractions were analyzed using ICP.

Imidazolium-organic solvent mixtures as electrolytes for lithium batteries

NASA Astrophysics Data System (ADS)

Chagnes, A.; Diaw, M.; Carré, B.; Willmann, P.; Lemordant, D.

γ-Butyrolactone (BL) has been mixed to the room temperature ionic liquid (RTIL) 1-butyl 3-methyl-imidazolium tetrafluoroborate (BMIBF 4) (ratio: 3/2, v/v) in the presence of lithium tetrafluoroborate (LiBF 4) for use as electrolyte in lithium-ion batteries. This mixture exhibits a larger thermal stability than the reference electrolyte EC/DEC/DMC (2/2/1) + LiPF 6 (1 M) and can be considered as a new RTIL as no free BL molecules are present in the liquid phase. The cycling ability of this electrolyte has been investigated at a graphite, a titanate oxide (Li 4Ti 5O 12) and a cobalt oxide (Li xCoO 2) electrodes. The ionic liquid is strongly reduced at the graphite electrode near 1 V and leads to the formation of a blocking film, which prevents any further cycling. The titanate oxide electrode can be cycled with a high capacity without any significant fading. Cycling of the positive cobalt oxide electrode was unsuccessfully owing to an oxidation reaction at the electrode surface, which prevents the intercalation or de-intercalation of Li ions in and from the host material. Less reactive cathode material than cobalt oxide must be employed with this RTIL.

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

Pasaribu, Marvin H., E-mail: marvin-shady88@yahoo.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id

Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li{sup +} ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anionmore » metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10{sup −2} S cm{sup −1} for chitosan to 1.30 × 10{sup −2} S cm{sup −1} for chitosan with EMImBF4/Li{sup +}, and this result was supported by analysis the surface morphology (SEM)« less

Lithium Metal-Copper Vanadium Oxide Battery with a Block Copolymer Electrolyte

DOE PAGES

Devaux, Didier; Wang, Xiaoya; Thelen, Jacob L.; ...

2016-09-08

Lithium (Li) batteries comprising multivalent positive active materials such as copper vanadium oxide have high theoretical capacity. These batteries with a conventional liquid electrolyte exhibit limited cycle life because of copper dissolution into the electrolyte. In this paper, we report here on the characterization of solid-state Li metal batteries with a positive electrode based on α-Cu 6.9V 6O 18.9 (α-CuVO 3). We replaced the liquid electrolyte by a nanostructured solid block copolymer electrolyte comprising of a mixture of polystyrene-b-poly(ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. In situ X-ray diffraction was used to follow the Li insertion/de-insertion mechanism into themore » α-CuVO 3 host material and its reversibility. In situ X-ray scattering revealed that the multistep electrochemical reactions involved are similar in the presence of liquid or solid electrolyte. The capacity fade of the solid-state batteries is less rapid than that of α-CuVO 3–Li metal batteries with a conventional liquid electrolyte. Hard X-ray microtomography revealed that upon cycling, voids and Cu-rich agglomerates were formed at the interface between the Li metal and the SEO electrolyte. Finally, the void volume and the volume occupied by the Cu-rich agglomerates were independent of C-rate and cycle number.« less

Soft X-ray emission spectroscopy of liquids and lithium batterymaterials

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

Augustsson, Andreas

2004-01-01

Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed tomore » view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools. In this thesis examples of studies of lithium battery electrodes and liquid systems using soft x-ray emission spectroscopy will be presented. Monochromatized synchrotron radiation has been used to accomplish selective excitation, in terms of energy and polarization. The electronic structure of graphite electrodes has been studied, before and after lithium intercalation. Changes in the electronic structure upon lithiation due to transfer of electrons into the graphite π-bands have been observed. Transfer of electrons in to the 3d states of transition metal oxides upon lithiation have been studied, through low energy excitations as dd- and charge transfer-excitations. A SEI was detected on cycled graphite electrodes. By the use of selective excitation different carbon sites were probed in the SEI. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell, to separate the liquid from the vacuum in the experimental chamber. Results from the study of liquid water showed a strong influence on the 3a1 molecular orbital and orbital mixing between water molecules upon hydrogen bonding. Apart from the four-hydrogen-bonding structure in water, a structure where one hydrogen bond is broken could be separated and identified. The soft x-ray emission study of methanol showed the existence of ring and chain formations in the liquid phase and the dominating structures are formed of 6 and 8 molecules. Upon mixing of the two liquids, a segregation at the molecular level was found and the formation of new structures, which could explain the unexpected low increase of the entropy.« 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 implantation at low temperature in silicon for sharp buried amorphous layer formation and defect engineering

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

Oliviero, E.; David, M. L.; Beaufort, M. F.

The crystalline-to-amorphous transformation induced by lithium ion implantation at low temperature has been investigated. The resulting damage structure and its thermal evolution have been studied by a combination of Rutherford backscattering spectroscopy channelling (RBS/C) and cross sectional transmission electron microscopy (XTEM). Lithium low-fluence implantation at liquid nitrogen temperature is shown to produce a three layers structure: an amorphous layer surrounded by two highly damaged layers. A thermal treatment at 400 Degree-Sign C leads to the formation of a sharp amorphous/crystalline interfacial transition and defect annihilation of the front heavily damaged layer. After 600 Degree-Sign C annealing, complete recrystallization takes placemore » and no extended defects are left. Anomalous recrystallization rate is observed with different motion velocities of the a/c interfaces and is ascribed to lithium acting as a surfactant. Moreover, the sharp buried amorphous layer is shown to be an efficient sink for interstitials impeding interstitial supersaturation and {l_brace}311{r_brace} defect formation in case of subsequent neon implantation. This study shows that lithium implantation at liquid nitrogen temperature can be suitable to form a sharp buried amorphous layer with a well-defined crystalline front layer, thus having potential applications for defects engineering in the improvement of post-implantation layers quality and for shallow junction formation.« less

New Electrode and Electrolyte Configurations for Lithium-Oxygen Battery.

PubMed

Ulissi, Ulderico; Elia, Giuseppe Antonio; Jeong, Sangsik; Reiter, Jakub; Tsiouvaras, Nikolaos; Passerini, Stefano; Hassoun, Jusef

2018-03-02

Cathode configurations reported herein are alternative to the most diffused ones for application in lithium-oxygen batteries, using an ionic liquid-based electrolyte. The electrodes employ high surface area conductive carbon as the reaction host, and polytetrafluoroethylene as the binding agent to enhance the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) reversibility. Roll-pressed, self-standing electrodes (SSEs) and thinner, spray deposited electrodes (SDEs) are characterized in lithium-oxygen cells using an ionic liquid (IL) based electrolyte formed by mixing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl)imide (DEMETFSI). The electrochemical results reveal reversible reactions for both electrode configurations, but improved electrochemical performance for the self-standing electrodes in lithium-oxygen cells. These electrodes show charge/discharge polarizations at 60 °C limited to 0.4 V, with capacity up to 1 mAh cm -2 and energy efficiency of about 88 %, while the spray deposited electrodes reveal, under the same conditions, a polarization of 0.6 V and energy efficiency of 80 %. The roll pressed electrode combined with the DEMETFSI-LiTFSI electrolyte and a composite Li x Sn-C alloy anode forms a full Li-ion oxygen cell showing extremely limited polarization, and remarkable energy efficiency. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A lithium-oxygen battery with a long cycle life in an air-like atmosphere.

PubMed

Asadi, Mohammad; Sayahpour, Baharak; Abbasi, Pedram; Ngo, Anh T; Karis, Klas; Jokisaari, Jacob R; Liu, Cong; Narayanan, Badri; Gerard, Marc; Yasaei, Poya; Hu, Xuan; Mukherjee, Arijita; Lau, Kah Chun; Assary, Rajeev S; Khalili-Araghi, Fatemeh; Klie, Robert F; Curtiss, Larry A; Salehi-Khojin, Amin

2018-03-21

Lithium-air batteries are considered to be a potential alternative to lithium-ion batteries for transportation applications, owing to their high theoretical specific energy. So far, however, such systems have been largely restricted to pure oxygen environments (lithium-oxygen batteries) and have a limited cycle life owing to side reactions involving the cathode, anode and electrolyte. In the presence of nitrogen, carbon dioxide and water vapour, these side reactions can become even more complex. Moreover, because of the need to store oxygen, the volumetric energy densities of lithium-oxygen systems may be too small for practical applications. Here we report a system comprising a lithium carbonate-based protected anode, a molybdenum disulfide cathode and an ionic liquid/dimethyl sulfoxide electrolyte that operates as a lithium-air battery in a simulated air atmosphere with a long cycle life of up to 700 cycles. We perform computational studies to provide insight into the operation of the system in this environment. This demonstration of a lithium-oxygen battery with a long cycle life in an air-like atmosphere is an important step towards the development of this field beyond lithium-ion technology, with a possibility to obtain much higher specific energy densities than for conventional lithium-ion batteries.

A Lithium-Air Battery Stably Working at High Temperature with High Rate Performance.

PubMed

Pan, Jian; Li, Houpu; Sun, Hao; Zhang, Ye; Wang, Lie; Liao, Meng; Sun, Xuemei; Peng, Huisheng

2018-02-01

Driven by the increasing requirements for energy supply in both modern life and the automobile industry, the lithium-air battery serves as a promising candidate due to its high energy density. However, organic solvents in electrolytes are likely to rapidly vaporize and form flammable gases under increasing temperatures. In this case, serious safety problems may occur and cause great harm to people. Therefore, a kind of lithium-air that can work stably under high temperature is desirable. Herein, through the use of an ionic liquid and aligned carbon nanotubes, and a fiber shaped design, a new type of lithium-air battery that can effectively work at high temperatures up to 140 °C is developed. Ionic liquids can offer wide electrochemical windows and low vapor pressures, as well as provide high thermal stability for lithium-air batteries. The aligned carbon nanotubes have good electric and heat conductivity. Meanwhile, the fiber format can offer both flexibility and weavability, and realize rapid heat conduction and uniform heat distribution of the battery. In addition, the high temperature has also largely improved the specific powers by increasing the ionic conductivity and catalytic activity of the cathode. Consequently, the lithium-air battery can work stably at 140 °C with a high specific current of 10 A g -1 for 380 cycles, indicating high stability and good rate performance at high temperatures. This work may provide an effective paradigm for the development of high-performance energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence of formation of lithium compounds on FTU tiles and dust

NASA Astrophysics Data System (ADS)

Ghezzi, F.; Laguardia, L.; Apicella, M. L.; Bressan, C.; Caniello, R.; Cippo, E. Perelli; Conti, C.; De Angeli, M.; Maddaluno, G.; Mazzitelli, G.

2018-01-01

Since 2006 lithium as an advanced plasma facing material has been tested on the Frascati Tokamak Upgrade (FTU). Lithium in the liquid phase acts both as plasma facing component, i.e. limiter, and plays also a role in plasma operation because by depositing a lithium film on the walls (lithization) oxygen is gettered. As in all deposition processes, even for the lithization, the presence of impurities in plasma phase strongly affects the properties of the deposited film. During the 2008 campaigns of FTU it was observed a strong release of carbon dioxide (during disruptions), resulting in successive serious difficulty of operation. In order to find the possible reactions occurred, we have analyzed the surface of two tiles of the toroidal limiter close to the Liquid Lithium Limiter (LLL). The presence of molybdenum oxides and carbides suggested that the surface temperatures could have exceeded 1000 K, likely during disruptions. lithium oxides and hydroxides have been found on the tiles and in the dust collected in the vessel, confirming the presence of LiO and LiOH and a not negligible concentration of Li2CO3 especially at the LLL location. On the basis of the above results, we propose here a simple rationale, based on a two reactions mechanism, which can explain the formation of Li2CO3 and its subsequent decomposition during disruption with release of CO2 in the vessel. Admitting surface temperatures above 1000 K during a disruption, relatively high partial pressures of CO2 are also predicted by the equilibrium constant for Li2CO3 decomposition.

Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects

DOE PAGES

Pascal, Tod A.; Villaluenga, Irune; Wujcik, Kevin H.; ...

2017-03-14

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ~30° below the expectedmore » freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.« less

Thermally-responsive, nonflammable phosphonium ionic liquid electrolytes for lithium metal batteries: operating at 100 degrees celsius† †Electronic supplementary information (ESI) available: Detailed ionic liquids synthesis, characterization, conductivity, cyclic voltammetry, battery cycling and those of other compositions; SEM images; energy density calculation. See DOI: 10.1039/c5sc01518a Click here for additional data file.

PubMed Central

Lin, X.; Kavian, R.; Lu, Y.; Hu, Q.; Shao-Horn, Y.

2015-01-01

Rechargeable batteries such as Li ion/Li metal batteries are widely used in the electronics market but the chemical instability of the electrolyte limits their use in more demanding environmental conditions such as in automotive, oil exploration, or mining applications. In this study, a series of alkyl phosphonium ionic liquid electrolyte are described with high thermal stability and solubility for LiTFSI. A lithium metal battery (LMB) containing a tailored phosphonium ionic liquid/LiTFSI electrolyte operates at 100 °C with good specific capacities and cycling stability. Substantial capacity is maintained during 70 cycles or 30 days. Instant on-off battery operation is realized via the significant temperature dependence of the electrolyte material, demonstrating the robustness and potential for use at high temperature. PMID:28757963

Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects.

PubMed

Pascal, Tod A; Villaluenga, Irune; Wujcik, Kevin H; Devaux, Didier; Jiang, Xi; Wang, Dunyang Rita; Balsara, Nitash; Prendergast, David

2017-04-12

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ∼30° below the expected freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.

Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids

NASA Astrophysics Data System (ADS)

Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi

2018-05-01

Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.

Ionic liquids and derived materials for lithium and sodium batteries.

PubMed

Yang, Qiwei; Zhang, Zhaoqiang; Sun, Xiao-Guang; Hu, Yong-Sheng; Xing, Huabin; Dai, Sheng

2018-03-21

The ever-growing demand for advanced energy storage devices in portable electronics, electric vehicles and large scale power grids has triggered intensive research efforts over the past decade on lithium and sodium batteries. The key to improve their electrochemical performance and enhance the service safety lies in the development of advanced electrode, electrolyte, and auxiliary materials. Ionic liquids (ILs) are liquids consisting entirely of ions near room temperature, and are characterized by many unique properties such as ultralow volatility, high ionic conductivity, good thermal stability, low flammability, a wide electrochemical window, and tunable polarity and basicity/acidity. These properties create the possibilities of designing batteries with excellent safety, high energy/power density and long-term stability, and also provide better ways to synthesize known materials. IL-derived materials, such as poly(ionic liquids), ionogels and IL-tethered nanoparticles, retain most of the characteristics of ILs while being endowed with other favourable features, and thus they have received a great deal of attention as well. This review provides a comprehensive review of the various applications of ILs and derived materials in lithium and sodium batteries including Li/Na-ion, dual-ion, Li/Na-S and Li/Na-air (O 2 ) batteries, with a particular emphasis on recent advances in the literature. Their unique characteristics enable them to serve as advanced resources, medium, or ingredient for almost all the components of batteries, including electrodes, liquid electrolytes, solid electrolytes, artificial solid-electrolyte interphases, and current collectors. Some thoughts on the emerging challenges and opportunities are also presented in this review for further development.

Composite electrolytes of polyethylene oxides/garnets interfacially wetted by ionic liquid for room-temperature solid-state lithium battery

NASA Astrophysics Data System (ADS)

Huo, Hanyu; Zhao, Ning; Sun, Jiyang; Du, Fuming; Li, Yiqiu; Guo, Xiangxin

2017-12-01

Paramount attention has been paid on solid polymer electrolytes due to their potential in enhancement of energy density as well as improvement of safety. Herein, the composite electrolytes consisting of Li-salt-free polyethylene oxides and 200 nm-sized Li6.4La3Zr1.4Ta0.6O12 particles interfacially wetted by [BMIM]TF2N of 1.8 μL cm-2 have been prepared. Such wetted ionic liquid remains the solid state of membrane electrolytes and decreases the interface impedance between the electrodes and the electrolytes. There is no release of the liquid phase from the PEO matrix when the pressure of 5.0 × 104 Pa being applied for 24 h. The interfacially wetted membrane electrolytes show the conductivity of 2.2 × 10-4 S cm-1 at 20 °C, which is one order of magnitude greater than that of the membranes without the wetted ionic liquids. The conduction mechanism is related to a large number of lithium ions releasing from Li6.4La3Zr1.4Ta0.6O12 particles and the improved conductive paths along the ion-liquid-wetted interfaces between the polymer matrix and ceramic grains. When the membranes being used in the solid-state LiFePO4/Li and LiFe0.15Mn0.85PO4/Li cells at 25 °C, the excellent rate capability and superior cycle stability has been shown. The results provide a new prospect for solid polymer electrolytes used for room-temperature solid-state lithium batteries.

Lithium dendrite growth through solid polymer electrolyte membranes

NASA Astrophysics Data System (ADS)

Harry, Katherine; Schauser, Nicole; Balsara, Nitash

2015-03-01

Replacing the graphite-based anode in current batteries with a lithium foil will result in a qualitative increase in the energy density of lithium batteries. The primary reason for not adopting lithium-foil anodes is the formation of dendrites during cell charging. In this study, stop-motion X-ray microtomography experiments were used to directly monitor the growth of lithium dendrites during electrochemical cycling of symmetric lithium-lithium cells with a block copolymer electrolyte. In an attempt to understand the relationship between viscoelastic properties of the electrolyte on dendrite formation, a series of complementary experiments including cell cycling, tomography, ac impedance, and rheology, were conducted above and below the glass transition temperature of the non-conducting poly(styrene) block; the conducting phase is a mixture of rubbery poly(ethylene oxide) and a lithium salt. The tomography experiments enable quantification of the evolution of strain in the block copolymer electrolyte. Our work provides fundamental insight into the dynamics of electrochemical deposition of metallic films in contact with high modulus polymer electrolytes. Rational approaches for slowing down and, perhaps, eliminating dendrite growth are proposed.

Structure factor of liquid alkali metals using a classical-plasma reference system

NASA Astrophysics Data System (ADS)

Pastore, G.; Tosi, M. P.

1984-06-01

This paper presents calculations of the liquid structure factor of the alkali metals near freezing, starting from the classical plasma of bare ions as reference liquid. The indirect ion-ion interaction arising from electronic screening is treated by an optimized random phase approximation (ORPA), imposing physical requirements as in the original ORPA scheme developed by Weeks, Chandler and Andersen for liquids with strongly repulsive core potentials. A comparison of the results with computer simulation data for a model of liquid rubidium shows that the present approach overcomes the well-known difficulties met in applying to these metals the standard ORPA based on a reference liquid of neutral hard spheres. The optimization scheme is also shown to be equivalent to a reduction of the range of the indirect interaction in momentum space, as proposed empirically in an earlier work. Comparison with experiment for the other alkalis shows that a good overall representation of the data can be obtained for sodium, potassium and cesium, but not for lithium, when one uses a very simple form of the electron-ion potential adjusted to the liquid compressibility. The small-angle scattering region is finally examined more carefully in the light of recent data of Waseda, with a view to possible refinements of the pseudopotential model.

Observations of the freeze/thaw performance of lithium fluoride by motion picture photography

NASA Technical Reports Server (NTRS)

Jaworske, D. A.; Perry, W. D.

1991-01-01

To gain direct observation of the molten salt phase change, a novel containerless technique was developed where the high surface tension of lithium fluoride was used to suspend a bead of the molten salt inside a specially designed wire cage. By varying the current passing through the wire, the cage also served as a variable heat source. In this way, the freeze/thaw performance of the lithium fluoride could be photographed by motion picture photography without the influence of container walls. The motion picture photography of the lithium fluoride sample revealed several zones during the phase change, a solid zone and a liquid zone, as expected, and a slush zone that was predicted by thermal analysis modeling.

Structure and crystallization of SiO2 and B2O3 doped lithium disilicate glasses from theory and experiment.

PubMed

Erlebach, Andreas; Thieme, Katrin; Sierka, Marek; Rüssel, Christian

2017-09-27

Solid solutions of SiO 2 and B 2 O 3 in Li 2 O·2SiO 2 are synthesized and characterized for the first time. Their structure and crystallization mechanisms are investigated employing a combination of simulations at the density functional theory level and experiments on the crystallization of SiO 2 and B 2 O 3 doped lithium disilicate glasses. The remarkable agreement of calculated and experimentally determined cell parameters reveals the preferential, kinetically controlled incorporation of [SiO 4 ] and [BO 4 ] at the Li + lattice sites of the Li 2 O·2SiO 2 crystal structure. While the addition of SiO 2 increases the glass viscosity resulting in lower crystal growth velocities, glasses containing B 2 O 3 show a reduction of both viscosities and crystal growth velocities. These observations could be rationalized by a change of the chemical composition of the glass matrix surrounding the precipitated crystal phase during the course of crystallization, which leads to a deceleration of the attachment of building units required for further crystal growth at the liquid-crystal interface.

Liquid lithium applications for solving challenging fusion reactor issues and NSTX-U contributions

DOE PAGES

Ono, M.; Jaworski, M. A.; Kaita, R.; ...

2016-08-05

Steady-state fusion reactor operation presents major divertor technology challenges, including high divertor heat flux both steady-state and transients. In addition to those issues, there are unresolved issues of long term dust accumulation and associated tritium inventory and safety issues. It has been suggested that radiative liquid lithium divertor concepts with a modest lithium-loop could provide a possible solution for these outstanding fusion reactor technology issues while potentially improving the reactor plasma performance. The application of lithium (Li) in NSTX resulted in improved H-mode confinement, H-mode power threshold reduction, and reduction in the divertor peak heat flux while maintaining essentially Li-freemore » core plasma operation even during H-modes. These promising results in NSTX and related modeling calculations motivated the radiative liquid lithium divertor (RLLD) concept and its variant, the active liquid lithium divertor concept (ARLLD), taking advantage of the enhanced Li radiation in relatively poorly confined divertor plasmas. It was estimated that only a few moles/sec of lithium injection would be needed to significantly reduce the divertor heat flux in a tokamak fusion power plant. By operating at lower temperatures ≤ 500°C than the first wall ~ 600 – 700°C, the LL-covered divertor chamber wall surfaces can serve as an effective particle pump, as impurities generally migrate toward lower temperature LL divertor surfaces. To maintain the LL purity, a closed LL loop system with a modest circulating capacity of ~ 1 liter/second (l/sec) is envisioned to sustain the steady-state operation of a 1 GW-electric class fusion power plant. By running the Li loop continuously, it can carry the dust particles and impurities generated in the vacuum vessel to outside where the dust / impurities are removed by relatively simple filter and cold/hot trap systems. Using a cold trap system, it can recover in tritium (T) in real time from LL at a rate of ~ 0.5 g / sec needed to sustain the fusion reaction while minimizing the T inventory issue. With an expected T fraction of ≤ 0.7 %, an acceptable level of T inventory can be achieved. In NSTX-U, preparations are now underway to elucidate the physics of Li plasma interactions with a number of Li application tools and Li radiation spectroscopic instruments. The NSTX-U Li evaporator which provides Li coating over the lower divertor plate, can offer important information on the RLLD concept, and the Li granule injector will test some of the key physics issue on the ARLLD concept. A LL-loop is also being prepared off line for prototyping future use on NSTX-U.« less

A solvated electron lithium electrode for secondary batteries

NASA Astrophysics Data System (ADS)

Sammells, A. F.; Semkow, K. W.

1986-09-01

Attention is given to a novel method for the achievement of high electro-chemical reversibility in Li-based nonaqueous cells, using a liquid negative electrode that consists of Li dissolved in liquid ammonia as a solvated electron Li electrode. The containment of this liquid negative active material from direct contact to a liquid nonaqueous electrolyte in the positive electrode compartment was realized through the use of a Li-intercalated, electronically conducting ceramic membrane.

Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

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

Kartini, Evvy; Manawan, Maykel

With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is stillmore » the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes, promise the potential to replace organic liquid electrolytes and thereby improve the safety of next-generation high-energy batteries. Li{sub 3}PO{sub 4} has been proved to be a good candidate for solid electrolyte, due to its easy in preparation, low cost, high melting temperature and good compatibility with the electrode materials. In the present work, Li{sub 3}PO{sub 4} has been prepared by wet chemical reaction, a simple method with the advantage of recycling a waste product H{sub 3}PO{sub 4}. The crystal structure has been characterized by both neutron and x-ray diffraction. The use of neutron scattering plays important role on observing the light atoms such as lithium ion. The x-ray diffraction results showed the crystal structure of orthorhombic phase P m n 21 (31), that belongs to the β-Li{sub 3}PO{sub 4}, with the lattice parameters are a = 6.123872, b = 5.250211, c = 4.876378. The conductivity of β-Li{sub 3}PO{sub 4} was around 10{sup −8} S/cm. Furthermore, the future application of the solid electrolyte layer in lithium ion battery will also be considered. It is concluded that the used of local resources on producing the solid electrolyte Li{sub 3}PO{sub 4} for lithium ion battery will give more added values to the researches and national industry.« less

Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes.

PubMed

Borodin, Oleg; Suo, Liumin; Gobet, Mallory; Ren, Xiaoming; Wang, Fei; Faraone, Antonio; Peng, Jing; Olguin, Marco; Schroeder, Marshall; Ding, Michael S; Gobrogge, Eric; von Wald Cresce, Arthur; Munoz, Stephen; Dura, Joseph A; Greenbaum, Steve; Wang, Chunsheng; Xu, Kang

2017-10-24

Using molecular dynamics simulations, small-angle neutron scattering, and a variety of spectroscopic techniques, we evaluated the ion solvation and transport behaviors in aqueous electrolytes containing bis(trifluoromethanesulfonyl)imide. We discovered that, at high salt concentrations (from 10 to 21 mol/kg), a disproportion of cation solvation occurs, leading to a liquid structure of heterogeneous domains with a characteristic length scale of 1 to 2 nm. This unusual nano-heterogeneity effectively decouples cations from the Coulombic traps of anions and provides a 3D percolating lithium-water network, via which 40% of the lithium cations are liberated for fast ion transport even in concentration ranges traditionally considered too viscous. Due to such percolation networks, superconcentrated aqueous electrolytes are characterized by a high lithium-transference number (0.73), which is key to supporting an assortment of battery chemistries at high rate. The in-depth understanding of this transport mechanism establishes guiding principles to the tailored design of future superconcentrated electrolyte systems.

Novel choline-based ionic liquids as safe electrolytes for high-voltage lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yong, Tianqiao; Zhang, Lingzhi; Wang, Jinglun; Mai, Yongjin; Yan, Xiaodan; Zhao, Xinyue

2016-10-01

Three choline-based ionic liquids functionalized with trimethylsilyl, allyl, and cynoethyl groups are synthesized in an inexpensive route as safe electrolytes for high-voltage lithium-ion batteries. The thermal stabilities, viscosities, conductivities, and electrochemical windows of these ILs are reported. Hybrid electrolytes were formulated by doping with 0.6 M LiPF6/0.4 M lithium oxalydifluoroborate (LiODFB) as salts and dimethyl carbonate (DMC) as co-solvent. By using 0.6 M LiPF6/0.4 M LiODFB trimethylsilylated choline-based IL (SN1IL-TFSI)/DMC as electrolyte, LiCoO2/graphite full cell showed excellent cycling performance with a capacity of 152 mAh g-1 and 99% capacity retention over 90 cycles at a cut-off voltage of 4.4 V. The propagation rate of SN1IL-TFSI)/DMC electrolyte is only one quarter of the commercial electrolyte (1 M LiPF6 EC/DEC/DMC, v/v/v = 1/1/1), suggesting a better safety feature.

Cycling performance of lithium metal polymer cells assembled with ionic liquid and poly(3-methyl thiophene)/carbon nanotube composite cathode

NASA Astrophysics Data System (ADS)

Kim, Dong-Won; Sivakkumar, S. R.; MacFarlane, Douglas R.; Forsyth, Maria; Sun, Yang-Kook

A poly(3-methylthiophene) (PMT)/multi-walled carbon nanotube (CNT) composite is synthesized by in situ chemical polymerization. The PMT/CNT composite is used as an active cathode material in lithium metal polymer cells assembled with ionic liquid (IL) electrolytes. The IL electrolyte consists of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4) and LiBF 4. A small amount of vinylene carbonate is added to the IL electrolyte to prevent the reductive decomposition of the imidazolium cation in EMIBF 4. A porous poly(vinylidene fluoride- co-hexafluoropropylene) (P(VdF- co-HFP)) film is used as a polymer membrane for assembling the cells. Electrochemical properties of the PMT/CNT composite electrode in the IL electrolyte are evaluated and the effect of vinylene carbonate on the cycling performance of the lithium metal polymer cells is investigated. The cells assembled with a non-flammable IL electrolyte and a PMT/CNT composite cathode are promising candidates for high-voltage-power sources with enhanced safety.

X-ray absorption spectroscopy of LiBF 4 in propylene carbonate. A model lithium ion battery electrolyte

DOE PAGES

Smith, Jacob W.; Lam, Royce K.; Sheardy, Alex T.; ...

2014-08-20

Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF 4 in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li + ion in thismore » model electrolyte. By generating linear combinations of the computed spectra of Li +-associating and free PC molecules and comparing to the experimental spectrum, we find a Li +–solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.« less

Develop a Low Cost, Safe and Environmentally Benign High Energy and High Rate Reserve Battery

DTIC Science & Technology

2004-09-30

Methylimidazolium hexafluorophosphate BMItrif 1-Butyl-3-Methylimidazolium trifluoromethanesulfonate EC Ethylene carbonate EMC Ethyl methyl carbonate DEC...ionic liquid, a new field in lithium -based batteries, merits special recognition. The contribution of Dr. Mark Salomon with respect to the...applications. In particular, the anode is typically metallic lithium , and the cathode depolarizer is, most commonly, thionyl chloride (SOCl2) or sulfuryl

A new ether-based electrolyte for dendrite-free lithium-metal based rechargeable batteries

PubMed Central

Miao, Rongrong; Yang, Jun; Xu, Zhixin; Wang, Jiulin; Nuli, Yanna; Sun, Limin

2016-01-01

A new ether-based electrolyte to match lithium metal electrode is prepared by introducing 1, 4-dioxane as co-solvent into lithium bis(fluorosulfonyl)imide/1,2-dimethoxyethane solution. Under the synergetic effect of solvents and salt, this simple liquid electrolyte presents stable Li cycling with dendrite-free Li deposition even at relatively high current rate, high coulombic efficiency of ca. 98%, and good anodic stability up to ~4.87 V vs Li RE. Its excellent performance will open up a new possibility for high energy-density rechargeable Li metal battery system. PMID:26878890

Zero-gravity growth of a sodium chloride-lithium fluoride eutectic mixture

NASA Technical Reports Server (NTRS)

Yue, A. S.; Yeh, C. W.; Yue, B. K.

1982-01-01

Continuous and discontinuous lithium fluoride fibers embedded in a sodium chloride matrix were produced in space and on Earth, respectively. The production of continuous fibers in a eutectic mixture was attributed to the absence of convective current in the liquid during solidification in space. Image transmission and optical transmittance measurements of transverse sections of the space-grown and Earth-grown ingots were made with a light microscope and a spectrometer. It was found that better optical properties were obtained from samples grown in space. This was attributed to a better alignment of lithium fluoride fibers along the growth direction.

Preliminary Evaluation of the Adequacy of Lithium Resources of the World and China for D-T Fusion Reactors

NASA Astrophysics Data System (ADS)

Wang, Yongliang; Ni, Muyi; Jiang, Jieqiong; Wu, Yican; FDS-Team

2012-07-01

This paper studied the adequacy of the World and China lithium resources, considering the most promising uses in the future, involving nuclear fusion and electric-vehicles. The lithium recycle model for D-T fusion power plant and electric-vehicles, and the logistic growth prediction model of the primary energy for the World and China were constructed. Based on these models, preliminary evaluation of lithium resources adequacy of the World and China for D-T fusion reactors was presented under certain assumptions. Results show that: a. The world terrestrial reserves of lithium seems too limited to support a significant D-T power program, but the lithium reserves of China are relatively abundant, compared with the world case. b. The lithium resources contained in the oceans can be called the “permanent" energy. c. The change in 6Li enrichment has no obvious effect on the availability period of the lithium resources using FDS-II (Liquid Pb-17Li breeder blanket) type of reactors, but it has a stronger effect when PPCS-B (Solid Li4 SiO4 ceramics breeder blanket) is used.

Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal

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

Pei, Allen; Zheng, Guangyuan; Shi, Feifei

Lithium metal has re-emerged as an exciting anode for high energy lithium-ion batteries due to its high specific capacity of 3860 mAh g -1 and lowest electrochemical potential of all known materials. However, lithium has been plagued by the issues of dendrite formation, high chemical reactivity with electrolyte, and infinite relative volume expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with lithium metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a criticalmore » fundamental scientific foundation of Li plating. Here, we study experimentally the morphology of lithium in the early stages of nucleation and growth on planar copper electrodes in liquid organic electrolyte. We elucidate the dependence of lithium nuclei size, shape, and areal density on current rate, consistent with classical nucleation and growth theory. We found that the nuclei size is proportional to the inverse of overpotential and the number density of nuclei is proportional to the cubic power of overpotential. Finally, based on this understanding, we propose a strategy to increase the uniformity of electrodeposited lithium on the electrode surface.« less

Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal

DOE PAGES

Pei, Allen; Zheng, Guangyuan; Shi, Feifei; ...

2017-01-10

Lithium metal has re-emerged as an exciting anode for high energy lithium-ion batteries due to its high specific capacity of 3860 mAh g -1 and lowest electrochemical potential of all known materials. However, lithium has been plagued by the issues of dendrite formation, high chemical reactivity with electrolyte, and infinite relative volume expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with lithium metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a criticalmore » fundamental scientific foundation of Li plating. Here, we study experimentally the morphology of lithium in the early stages of nucleation and growth on planar copper electrodes in liquid organic electrolyte. We elucidate the dependence of lithium nuclei size, shape, and areal density on current rate, consistent with classical nucleation and growth theory. We found that the nuclei size is proportional to the inverse of overpotential and the number density of nuclei is proportional to the cubic power of overpotential. Finally, based on this understanding, we propose a strategy to increase the uniformity of electrodeposited lithium on the electrode surface.« less

Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal.

PubMed

Pei, Allen; Zheng, Guangyuan; Shi, Feifei; Li, Yuzhang; Cui, Yi

2017-02-08

Lithium metal has re-emerged as an exciting anode for high energy lithium-ion batteries due to its high specific capacity of 3860 mAh g -1 and lowest electrochemical potential of all known materials. However, lithium has been plagued by the issues of dendrite formation, high chemical reactivity with electrolyte, and infinite relative volume expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with lithium metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a critical fundamental scientific foundation of Li plating. Here, we study experimentally the morphology of lithium in the early stages of nucleation and growth on planar copper electrodes in liquid organic electrolyte. We elucidate the dependence of lithium nuclei size, shape, and areal density on current rate, consistent with classical nucleation and growth theory. We found that the nuclei size is proportional to the inverse of overpotential and the number density of nuclei is proportional to the cubic power of overpotential. Based on this understanding, we propose a strategy to increase the uniformity of electrodeposited lithium on the electrode surface.

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.

Thermodynamically constrained correction to ab initio equations of state

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

French, Martin; Mattsson, Thomas R.

2014-07-07

We show how equations of state generated by density functional theory methods can be augmented to match experimental data without distorting the correct behavior in the high- and low-density limits. The technique is thermodynamically consistent and relies on knowledge of the density and bulk modulus at a reference state and an estimation of the critical density of the liquid phase. We apply the method to four materials representing different classes of solids: carbon, molybdenum, lithium, and lithium fluoride. It is demonstrated that the corrected equations of state for both the liquid and solid phases show a significantly reduced dependence ofmore » the exchange-correlation functional used.« less

Demonstration of an electrochemical liquid cell for operando transmission electron microscopy observation of the lithiation/delithiation behavior of Si nanowire battery anodes.

PubMed

Gu, Meng; Parent, Lucas R; Mehdi, B Layla; Unocic, Raymond R; McDowell, Matthew T; Sacci, Robert L; Xu, Wu; Connell, Justin Grant; Xu, Pinghong; Abellan, Patricia; Chen, Xilin; Zhang, Yaohui; Perea, Daniel E; Evans, James E; Lauhon, Lincoln J; Zhang, Ji-Guang; Liu, Jun; Browning, Nigel D; Cui, Yi; Arslan, Ilke; Wang, Chong-Min

2013-01-01

Over the past few years, in situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration-the dynamics of the electrolyte and, potentially, a future quantitative characterization of the solid electrolyte interphase layer formation and structural and chemical evolution.

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.

Interphase Evolution of a Lithium-Ion/Oxygen Battery.

PubMed

Elia, Giuseppe Antonio; Bresser, Dominic; Reiter, Jakub; Oberhumer, Philipp; Sun, Yang-Kook; Scrosati, Bruno; Passerini, Stefano; Hassoun, Jusef

2015-10-14

A novel lithium-ion/oxygen battery employing Pyr14TFSI-LiTFSI as the electrolyte and nanostructured LixSn-C as the anode is reported. The remarkable energy content of the oxygen cathode, the replacement of the lithium metal anode by a nanostructured stable lithium-alloying composite, and the concomitant use of nonflammable ionic liquid-based electrolyte result in a new and intrinsically safer energy storage system. The lithium-ion/oxygen battery delivers a stable capacity of 500 mAh g(-1) at a working voltage of 2.4 V with a low charge-discharge polarization. However, further characterization of this new system by electrochemical impedance spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy reveals the progressive decrease of the battery working voltage, because of the crossover of oxygen through the electrolyte and its direct reaction with the LixSn-C anode.

Cu3V2O8 hollow spheres in photocatalysis and primary lithium batteries

NASA Astrophysics Data System (ADS)

Zhang, Shaoyan; Sun, Yan; Li, Chunsheng; Ci, Lijie

2013-11-01

In this paper, Cu3V2O8 hollow spheres have been successfully synthesized via a liquid precipitation method with colloidal carbon spheres as template followed by a subsequent heat treatment process. On the basis of XRD analysis, SEM observation, and TG-DSC analysis of the precursor and products, the formation mechanism of Cu3V2O8 hollow spheres was proposed. UV-vis diffuse reflectance spectra showed that the Cu3V2O8 hollow spheres exhibit strong absorption in a wide wavelength range from UV to visible light. The photocatalytic activity experiment indicated that the as-prepared Cu3V2O8 hollow spheres exhibited good photocatalytic activity in degradation of methyl orange (MO) under 150-W xenon arc lamp light irradiation. Furthermore, electrochemical measurements showed that the Cu3V2O8 hollow spheres exhibited high discharge capacity and excellent high-rate capability, indicating potential cathode candidates for primary lithium batteries used in long-term implantable cardiac defibrillators (ICDs).

Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature.

PubMed

Lin, Xinrong; Chapman Varela, Jennifer; Grinstaff, Mark W

2016-12-20

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 °C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.

Novel Approach for in Situ Recovery of Lithium Carbonate from Spent Lithium Ion Batteries Using Vacuum Metallurgy.

PubMed

Xiao, Jiefeng; Li, Jia; Xu, Zhenming

2017-10-17

Lithium is a rare metal because of geographical scarcity and technical barrier. Recycling lithium resource from spent lithium ion batteries (LIBs) is significant for lithium deficiency and environmental protection. A novel approach for recycling lithium element as Li 2 CO 3 from spent LIBs is proposed. First, the electrode materials preobtained by mechanical separation are pyrolyzed under enclosed vacuum condition. During this process the Li is released as Li 2 CO 3 from the crystal structure of lithium transition metal oxides due to the collapse of the oxygen framework. An optimal Li recovery rate of 81.90% is achieved at 973 K for 30 min with a solid-to-liquid ratio of 25 g L -1 , and the purity rate of Li 2 CO 3 is 99.7%. The collapsed mechanism is then presented to explain the release of lithium element during the vacuum pyrolysis. Three types of spent LIBs including LiMn 2 O 4 , LiCoO 2 , and LiCo x Mn y Ni z O 2 are processed to prove the validity of in situ recycling Li 2 CO 3 from spent LIBs under enclosed vacuum condition. Finally, an economic assessment is taken to prove that this recycling process is positive.

Neutronics Evaluation of Lithium-Based Ternary Alloys in IFE Blankets

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

Jolodosky, A.; Fratoni, M.

2014-11-20

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

Liquid li structure and dynamics: A comparison between OFDFT and second nearest-neighbor embedded-atom method

DOE PAGES

Chen, Mohan; Vella, Joseph R.; Panagiotopoulos, Athanassios Z.; ...

2015-04-08

The structure and dynamics of liquid lithium are studied using two simulation methods: orbital-free (OF) first-principles molecular dynamics (MD), which employs OF density functional theory (DFT), and classical MD utilizing a second nearest-neighbor embedded-atom method potential. The properties we studied include the dynamic structure factor, the self-diffusion coefficient, the dispersion relation, the viscosity, and the bond angle distribution function. Our simulation results were compared to available experimental data when possible. Each method has distinct advantages and disadvantages. For example, OFDFT gives better agreement with experimental dynamic structure factors, yet is more computationally demanding than classical simulations. Classical simulations can accessmore » a broader temperature range and longer time scales. The combination of first-principles and classical simulations is a powerful tool for studying properties of liquid lithium.« less

A vanadium alloy for the application in a liquid metal blanket of a fusion reactor

NASA Astrophysics Data System (ADS)

Borgstedt, H. U.; Grundmann, M.; Konys, J.; Perić, Z.

1988-07-01

The vanadium alloy V3Ti1Si has been corrosion tested in liquid lithium and the eutectic alloy Pb-17Li at 550°C. This alloy has a comparable corrosion resistance to the alloy V15Cr5Ti in lithium. In this molten metal it is superior to stainless steel AISI 316. In the Pb-17Li melt it is even superior to martensitic steels. The alloy has only a weak tendency to be dissolved. It is sensitive to an exchange of non-metallic elements, which causes the formation of a hardened surface layer. These chemical effects are influenced by the mass and surface ratios of the vanadium alloy to the molten metals and other structural materials. These ratios are unfavorable in the two test loops. The effects might be less pronounced in a vanadium alloy/liquid metal fusion reactor blanket.

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

NASA Technical Reports Server (NTRS)

Hernandez-Lugo, Dionne M.; Wu, James; Bennett, William; Ming, Yu; Zhu, Yu

2015-01-01

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Reddy, V. Prakash; Prakash, G. K. Syria; Hu, Jinbo; Yan, Ping; Smart, Marshall; Bugga, ratnakumar; Chin, Keith; Surampudi, Subarao

2008-01-01

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Functional materials for breeding blankets—status and developments

NASA Astrophysics Data System (ADS)

Konishi, S.; Enoeda, M.; Nakamichi, M.; Hoshino, T.; Ying, A.; Sharafat, S.; Smolentsev, S.

2017-09-01

The development of tritium breeder, neutron multiplier and flow channel insert materials for the breeding blanket of the DEMO reactor is reviewed. Present emphasis is on the ITER test blanket module (TBM); lithium metatitanate (Li2TiO3) and lithium orthosilicate (Li4SiO4) pebbles have been developed by leading TBM parties. Beryllium pebbles have been selected as the neutron multiplier. Good progress has been made in their fabrication; however, verification of the design by experiments is in the planning stage. Irradiation data are also limited, but the decrease in thermal conductivity of beryllium due to irradiation followed by swelling is a concern. Tests at ITER are regarded as a major milestone. For the DEMO reactor, improvement of the breeder has been attempted to obtain a higher lithium content, and Be12Ti and other beryllide intermetallic compounds that have superior chemical stability have been studied. LiPb eutectic has been considered as a DEMO blanket in the liquid breeder option and is used as a coolant to achieve a higher outlet temperature; a SiC flow channel insert is used to prevent magnetohydrodynamic pressure drop and corrosion. A significant technical gap between ITER TBM and DEMO is recognized, and the world fusion community is working on ITER TBM and DEMO blanket development in parallel.

Measurements of optical properties of some molten oxides

NASA Astrophysics Data System (ADS)

Nason, D. O.; Yen, C. T.; Tiller, W. A.

1990-11-01

A method based on a fine-focussed optical laser has been developed to measure the spectral reflectance and the transmittance of small ( ∽ 1 mm) liquid or single crystal materials. The measured normal spectral emittance for 633 nm light is about 0.9 for several molten refractory oxides, 0.8 for lithium niobate and 0.7 for molten sapphire. Sapphire and YAG experience a several-fold increase in emittance on melting. The absorption coefficient and the thickness for opaqueness are calculated and some consequences of the partial transparency of small hot materials, when their temperatures are measured by optical pyrometry, are discussed.

Oxidation reaction of polyether-based material and its suppression in lithium rechargeable battery using 4 V class cathode, LiNi1/3Mn1/3Co1/3O2.

PubMed

Kobayashi, Takeshi; Kobayashi, Yo; Tabuchi, Masato; Shono, Kumi; Ohno, Yasutaka; Mita, Yuichi; Miyashiro, Hajime

2013-12-11

The all solid-state lithium battery with polyether-based solid polymer electrolyte (SPE) is regarded as one of next-generation lithium batteries, and has potential for sufficient safety because of the flammable-electrolyte-free system. It has been believed that polyether-based SPE is oxidized at the polymer/electrode interface with 4 V class cathodes. Therefore, it has been used for electric devices such as organic transistor, and lithium battery under 3 V. We estimated decomposition reaction of polyether used as SPE of all solid-state lithium battery. We first identified the decomposed parts of polyether-based SPE and the conservation of most main chain framework, considering the results of SPE analysis after long cycle operations. The oxidation reaction was found to occur slightly at the ether bond in the main chain with the branched side chain. Moreover, we resolved the issue by introducing a self-sacrificing buffer layer at the interface. The introduction of sodium carboxymethyl cellulose (CMC) to the 4 V class cathode surface led to the suppression of SPE decomposition at the interface as a result of the preformation of a buffer layer from CMC, which was confirmed by the irreversible exothermic reaction during the first charge, using electrochemical calorimetry. The attained 1500 cycle operation is 1 order of magnitude longer than those of previously reported polymer systems, and compatible with those of reported commercial liquid systems. The above results indicate to proceed to an intensive research toward the realization of 4 V class "safe" lithium polymer batteries without flammable liquid electrolyte.

Innovative Surfaces for Controlled Flow of Liquid Metal

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

Fortini, Arthur J.

2016-03-22

The potential economic, environmental, and strategic benefits associated with the development of fusion energy are numerous. However, application of fusion technology cannot be realized until advanced materials are developed that allow operation under the high heat flux conditions necessary for cost-competitive electric energy generation. Bathing the wall of a fusion reactor plasma-facing component in a liquid metal such as lithium, gallium, or tin is a viable approach for accommodating continuous heat flux levels exceeding 10 MW/m2, and it is also the preferred approach for removing hydrogen isotopes. Stabilizing the liquid film is the key challenge, which can be addressed throughmore » the use of a microtextured surface. In previous work, Ultramet developed high temperature microtextured tungsten and rhenium coatings consisting of thousands of high aspect ratio pyramids per square millimeter that are compatible with lithium, gallium, and tin, and whose effectiveness in wicking molten lithium has been demonstrated even in the presence of strong body forces. Heat transfer and fluid flow characteristics were also modeled. Because of the safety issues surrounding lithium, the current project focused on adapting and optimizing this wicking technology for use with gallium and tin. The coatings were deposited by chemical vapor deposition (CVD), and the height, population density, and morphology of the pyramids was varied to optimize the wetting properties, which were measured and quantified by exposing the coatings to molten gallium or tin. Micron-thick films of other materials were also applied to the textured surfaces to vary the wetting characteristics. Wicking tests were performed with both gallium and tin on a variety of coatings with different textures and surface chemistries, and both metals showed excellent wicking and wettability on virtually all of the textured coatings. Extensive modeling of the interaction between the dendrites and the liquid metal, as well as additional wetting testing, was performed by Digital Materials Solutions (DMS, Carlsbad, CA).« less

Lithium Sorption from Simulated Geothermal Brine: Impact of pH, Temperature, and Brine Chemistry

DOE Data Explorer

Jay Renew

2016-02-06

Lithium sorption information from experiments. Data includes the effects of pH, temperature and brine chemistry on the sorption of Lithium from a simulated geothermal brine. The sorbent used in the experiments is "hydrothermally produced, Spinel-LiMn2O4". The sorbent was produced by Carus Corporation.

Characterization of reactive tracers for C-wells field experiments 1: Electrostatic sorption mechanism, lithium

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

Fuentes, H.R.; Polzer, W.L.; Essington, E.H.

1989-11-01

Lithium (Li{sup +}) was introduced as lithium bromide (LiBr), as a retarded tracer for experiments in the C-wells complex at Yucca Mountain, Nevada Test Site, Nevada. The objective was to evaluate the potential of lithium to sorb predominately by physical forces. lithium was selected as a candidate tracer on the basis of high solubility, good chemical and biological stability, and relatively low sorptivity; lack of bioaccumulation and exclusion as a priority pollutant in pertinent federal environmental regulations; good analytical detectability and low natural background concentrations; and a low cost Laboratory experiments were performed with suspensions of Prow Pass cuttings frommore » drill hole UE-25p{number_sign}1 at depths between 549 and 594 m in J-13 water at a pH of approximately 8 and in the temperature range of 25{degree}C to 45{degree}C. Batch equilibrium and kinetics experiments were performed; estimated thermodynamic constants, relative behavior between adsorption and desorption, and potentiometric studies provided information to infer the physical nature of lithium sorption.« less

Vertically-aligned carbon nanotubes on aluminum as a light-weight positive electrode for lithium-polysulfide batteries.

PubMed

Liatard, S; Benhamouda, K; Fournier, A; Ramos, R; Barchasz, C; Dijon, J

2015-05-04

A light-weight, high specific surface current collector made of vertically-aligned carbon nanotubes grown on an aluminum substrate was fabricated and studied as a positive electrode in a semi-liquid lithium/polysulfide battery. This simple system delivered stable capacities over 1000 mA h gS(-1) and 2 mA h cm(-2) with almost no capacity loss over 50 cycles.

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...

Freeze-Dried Sulfur-Graphene Oxide-Carbon Nanotube Nanocomposite for High Sulfur-Loading Lithium/Sulfur Cells.

PubMed

Hwa, Yoon; Seo, Hyeon Kook; Yuk, Jong-Min; Cairns, Elton J

2017-11-08

The ambient-temperature rechargeable lithium/sulfur (Li/S) cell is a strong candidate for the beyond lithium ion cell since significant progress on developing advanced sulfur electrodes with high sulfur loading has been made. Here we report on a new sulfur electrode active material consisting of a cetyltrimethylammonium bromide-modified sulfur-graphene oxide-carbon nanotube (S-GO-CTA-CNT) nanocomposite prepared by freeze-drying. We show the real-time formation of nanocrystalline lithium sulfide (Li 2 S) at the interface between the S-GO-CTA-CNT nanocomposite and the liquid electrolyte by in situ TEM observation of the reaction. The combination of GO and CNT helps to maintain the structural integrity of the S-GO-CTA-CNT nanocomposite during lithiation/delithiation. A high S loading (11.1 mgS/cm 2 , 75% S) S-GO-CTA-CNT electrode was successfully prepared using a three-dimensional structured Al foam as a substrate and showed good S utilization (1128 mAh/g S corresponding to 12.5 mAh/cm 2 ), even with a very low electrolyte to sulfur weight ratio of 4. Moreover, it was demonstrated that the ionic liquid in the electrolyte improves the Coulombic efficiency and stabilizes the morphology of the Li metal anode.

Ionic Liquid-Enhanced Solid State Electrolyte Interface (SEI) for Lithium Sulfur Batteries

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

Zheng, Jianming; Gu, Meng; Chen, Honghao

2013-05-16

Li-S battery is a complicated system with many challenges existing before its final market penetration. While most of the reported work for Li-S batteries is focused on the cathode design, we demonstrate in this work that the anode consumption accelerated by corrosive polysulfide solution also critically determines the Li-S cell performance. To validate this hypothesis, ionic liquid (IL) N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Py14TFSI) has been employed to modify the properties of SEI layer formed on Li metal surface in Li-S batteries. It is found that the IL-enhanced passivation film on the lithium anode surface exhibits much different morphology and chemical compositions, effectivelymore » protecting lithium metal from continuous attack by soluble polysulfides. Therefore, both cell impedance and the irreversible consumption of polysulfides on lithium metal are reduced. As a result, the Coulombic efficiency and the cycling stability of Li-S batteries have been greatly improved. After 120 cycles, Li-S battery cycled in the electrolyte containing IL demonstrates a high capacity retention of 94.3% at 0.1 C rate. These results unveil another important failure mechanism for Li-S batteries and shin the light on the new approaches to improve Li-S battery performances.« less

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.

Development of a high-power neutron-producing lithium target for boron neutron capture therapy

NASA Astrophysics Data System (ADS)

Brown, Adam V.; Scott, Malcolm C.

2000-12-01

A neutron producing lithium target for a novel, accelerator based cancer treatment requires the removal of up to 6kW of heat produced by 1-2mA beam of 2.3-3.0MeV protons. This paper presents the results form computer simulations which show that, using submerged jet cooling, a solid lithium target can be maintained up to 1.6mA, and a liquid target up to 2.6mA, assuming a 3.0MeV proton beam. The predictions from the simulations are verified through the use of an experimental heat transfer test-rig and the result form a number of metallurgical studies made to select a compatible substrate material for the lithium are reported.

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.

Excess lithium salt functions more than compensating for lithium loss when synthesizing Li6.5La3Ta0.5Zr1.5O12 in alumina crucible

NASA Astrophysics Data System (ADS)

Liu, Kai; Ma, Jiang-Tao; Wang, Chang-An

2014-08-01

Garnet type electrolyte "Li6.5La3Ta0.5Zr1.5O12" (LLZTO) was prepared by conventional solid-state reaction in alumina crucibles and excess lithium salt (from 0% to 50 mol%) was added into the starting materials to investigate the effects of excess lithium salt on the property of LLZTO. SEM, XRD and AC impedance were used to determine the microstructure, phase formation and Li-ion conductivity. Cubic garnet with a minor second phase LiAlO2 in the grain boundary was obtained for the pellets with excess lithium salt. As the amount of excess lithium salt increased, more Al element diffused from alumina crucibles to LLZTO pellets and reacted with excess lithium salt to form liquid Li2O-Al2O3 phase in the grain boundary, which accelerated the pellets' densification and reduced lithium loss at a high temperature. Ionic conductivity of LLZTO pellets increased with the amount of excess lithium salt added and leveled off at ∼4 × 10-4 S cm-1 when lithium salt exceeded 30 mol%. The performance of Li-air batteries with hybrid electrolytes, using homemade LLZTO thin pellets as solid electrolytes, was investigated. The LLZTO thin pellet with more excess lithium salt in starting material had a higher density and resulted in better cell performance.

Investigating Electrochemical Processes in Secondary Batteries

NASA Astrophysics Data System (ADS)

Cama, Christina A.

For the past twenty-six years, the lithium-ion battery has been the most popular recharge- able battery for portable devices and electric vehicles. Despite its success, the energy storage capability of lithium-ion batteries (LIBs) is significantly limited by both the electrodes and electrolytes employed. Typical LIBs rely on intercalation-type electrodes, that are not capable of storing more than 1 Li+ per formula unit. The energy storage capability of LIBs can be improved through the application of conversion-type materials and beyond lithium chemistries. This research involves multiple projects which explore the electrochemistry of conversion electrodes, magnesium-ion chemistry, and lithium-sulfur chemistry. Application of conversion-electrodes like copper ferrite, CuFe2O4, and magnetite, Fe3O4, are capable of lithium storage over five times greater than that achieved by electrodes used in commercial LIBs. The drawback to utilizing the conversion mechanism is that significant energy storage capability is lost during charge. In this research, X- ray characterization methods, including X-ray Diffraction (XRD) and X-ray Absorption Spectroscopy (XAS) are used to elucidate the lithiation and delithiation mechanism for CuFe2O4 and to understand the source of the irreversibility. These experiments provide significant insight into the reduction processes and cation migration within the structure. During lithiation, CuFe2O4 undergoes a three-step reduction mechanism involving (1) lithiation of CuFe2O4, (2) extrusion of copper metal nanoparticles and formation of rock- salt LiFeO2, followed by the (3) formation of iron metal nanoparticles. Upon delithiation, XAS spectra clearly demonstrate the feasibility of Fe0 oxidation to a rock-salt iron oxide; however, Cu0 oxidation is not observed. Additional experiments explored the kinetic limitations of lithiating Fe3O4 nanoparticles, with different crystallite sizes. The experiments demonstrate that the kinetics of the lithiation mechanism are influenced by the electroactive material’s agglomerate and crystallite size. The rate of lithiation involving small crystallites is dependent on diffusion within the agglomerates; however, as the crystallite size increases, the lithiation rate is inhibited by diffusion within both the agglomerate and the crystallite. Battery chemistries beyond lithium can also lead to energy storage capabilities an order of magnitude higher than LIBs. Both magnesium-ion and lithium-sulfur battery chemistries are investigated in this dissertation. The properties of ionic liquid electrolytes are explored as safer alternatives to harmful Grignard-reagent electrolytes commonly used for magnesium chemistries. Electrochemical evaluation of the ionic liquid electrolytes found that although better conductivity can be achieved with unsaturated electrolytes like imidizolium based electrolytes, greater oxidative voltages are possible with saturated electrolytes like the piperidinium and pyridinium based electrolytes. The higher oxidative voltage is a promising attribute for high voltage applications. Cathode additives, including FeS2 and microporous carbon, are studied to inhibit polysulfide dissolution within the electrolyte of Li|S batteries. Although FeS2 exhibited promising electrochemistry as its own cathode, it was found to be an ineffective additive within sulfur cathodes. Instead, the properties of microporous carbons are explored to identify an appropriate carbon additive to both increase conductivity and impede polysulfide dissolution. A wood based carbon exhibited high capacity and long cycle life at low rate compared to conventional microporous carbons. As a whole, this research has provided valuable insight into the electrochemical processes taking place within a battery, as well as the factors which affect these processes. Electrochemical, spectroscopic, and various scattering methods are used to probe processes which span from the reactions occurring within the electrode to the redox reactions which define the voltage limitations of the electrolyte. These studies demonstrate the impact of each battery component on the overall electrochemical performance and provide fundamental insight into battery operation.

Characterization of lithium coordination sites with magic-angle spinning NMR

NASA Astrophysics Data System (ADS)

Haimovich, A.; Goldbourt, A.

2015-05-01

Lithium, in the form of lithium carbonate, is one of the most common drugs for bipolar disorder. Lithium is also considered to have an effect on many other cellular processes hence it possesses additional therapeutic as well as side effects. In order to quantitatively characterize the binding mode of lithium, it is required to identify the interacting species and measure their distances from the metal center. Here we use magic-angle spinning (MAS) solid-state NMR to study the binding site of lithium in complex with glycine and water (LiGlyW). Such a compound is a good enzyme mimetic since lithium is four-coordinated to one water molecule and three carboxylic groups. Distance measurements to carbons are performed using a 2D transferred echo double resonance (TEDOR) MAS solid-state NMR experiment, and water binding is probed by heteronuclear high-resolution proton-lithium and proton-carbon correlation (wPMLG-HETCOR) experiments. Both HETCOR experiments separate the main complex from impurities and non-specifically bound lithium species, demonstrating the sensitivity of the method to probe the species in the binding site. Optimizations of the TEDOR pulse scheme in the case of a quadrupolar nucleus with a small quadrupole coupling constant show that it is most efficient when pulses are positioned on the spin-1/2 (carbon-13) nucleus. Since the intensity of the TEDOR signal is not normalized, careful data analysis that considers both intensity and dipolar oscillations has to be performed. Nevertheless we show that accurate distances can be extracted for both carbons of the bound glycine and that these distances are consistent with the X-ray data and with lithium in a tetrahedral environment. The lithium environment in the complex is very similar to the binding site in inositol monophosphatase, an enzyme associated with bipolar disorder and the putative target for lithium therapy. A 2D TEDOR experiment applied to the bacterial SuhB gene product of this enzyme was designed to probe direct correlations between lithium, the enzyme inhibitor, and the closest carboxyl carbons of the binding site. At this point, the chemical shift of the bound carboxyl groups in this 29 kDa enzyme could be determined.

Imprintable, bendable, and shape-conformable polymer electrolytes for versatile-shaped lithium-ion batteries.

PubMed

Kil, Eun-Hye; Choi, Keun-Ho; Ha, Hyo-Jeong; Xu, Sheng; Rogers, John A; Kim, Mi Ri; Lee, Young-Gi; Kim, Kwang Man; Cho, Kuk Young; Lee, Sang-Young

2013-03-13

A class of imprintable, bendable, and shape-conformable polymer electrolyte with excellent electrochemical performance in a lithium battery system is reported. The material consists of a UV-cured polymer matrix, high-boiling point liquid electrolyte, and Al2 O3 nanoparticles, formulated for use in lithium-ion batteries with 3D-structured electrodes or flexible characteristics. The unique structural design and well-tuned rheological characteristics of the UV-curable electrolyte mixture, in combination with direct UV-assisted nanoimprint lithography, allow the successful fabrication of polymer electrolytes in geometries not accessible with conventional materials. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

RARE-EARTH METAL FISSION PRODUCTS FROM LIQUID U-Bi

DOEpatents

Wiswall, R.H.

1960-05-10

Fission product metals can be removed from solution in liquid bismuth without removal of an appreciable quantity of uranium by contacting the liquid metal solution with fused halides, as for example, the halides of sodium, potassium, and lithium and by adding to the contacted phases a quantity of a halide which is unstable relative to the halides of the fission products, a specific unstable halide being MgCl/sub 3/.

On the Development of Hydrogen Isotope Extraction Technologies for a Full LiMIT-Style PFC Liquid Lithium Loop

NASA Astrophysics Data System (ADS)

Christenson, Michael; Szott, Matthew; Stemmley, Steven; Mettler, Jeremy; Wendeborn, John; Moynihan, Cody; Ahn, Chisung; Andruczyk, Daniel; Ruzic, David

2017-10-01

Lithium has proven over numerous studies to improve core confinement, allowing access to operational regimes previously unattainable when using solid, high-Z divertor and limiter modules in magnetic confinement devices. Lithium readily absorbs fuel species, and while this is advantageous, it is also detrimental with regards to tritium inventory and safety concerns. As such, extraction technologies for the recovery of hydrogenic isotopes captured by lithium require development and testing in the context of a larger lithium loop recycling system. Proposed reclamation technologies at the University of Illinois at Urbana-Champaign (UIUC) will take advantage of the thermophysical properties of the lithium-hydrogen-lithium hydride system as the driving force for recovery. Previous work done at UIUC indicates that hydrogen release from pure lithium hydride reaches a maximum of 7 x 1018 s-1 at 665 °C. While this recovery rate is appreciable, reactor-scale scenarios will require isotope recycling to happen on an even faster timescale. The ratio of isotope dissolution to hydride precipitate formation must therefore be determined, along with the energy needed to recoup trapped hydrogen isotopes. Extraction technologies for use with a LiMIT-style loop system will be discussed and results will be presented. DOE/ALPS DE-FG02-99ER54515.

Targeting adequate thermal stability and fire safety in selecting ionic liquid-based electrolytes for energy storage.

PubMed

Chancelier, L; Diallo, A O; Santini, C C; Marlair, G; Gutel, T; Mailley, S; Len, C

2014-02-07

The energy storage market relating to lithium based systems regularly grows in size and expands in terms of a portfolio of energy and power demanding applications. Thus safety focused research must more than ever accompany related technological breakthroughs regarding performance of cells, resulting in intensive research on the chemistry and materials science to design more reliable batteries. Formulating electrolyte solutions with nonvolatile and hardly flammable ionic liquids instead of actual carbonate mixtures could be safer. However, few definitions of thermal stability of electrolytes based on ionic liquids have been reported in the case of abuse conditions (fire, shortcut, overcharge or overdischarge). This work investigates thermal stability up to combustion of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C1C4Im][NTf2]) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([PYR14][NTf2]) ionic liquids, and their corresponding electrolytes containing lithium bis(trifluoromethanesulfonyl)imide LiNTf2. Their possible routes of degradation during thermal abuse testings were investigated by thermodynamic studies under several experimental conditions. Their behaviours under fire were also tested, including the analysis of emitted compounds.

Irreversible Capacities of Graphite in Low Temperature Electrolytes for Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Ratnakumar, B.; Smart, M.; Surampudi, S.; Wang, Y.; Zhang, X.; Greenbaum, S.; Hightower, A.; Ahn, C.; Fultz, B.

1999-01-01

Carbonaceous anode materials in lithium ion rechargeable cells experience irreversible capacity, mainly due to a consumption of lithium in the formation of surface passive films. The stability and kinetics of lithium intercalation into the carbon anodes are dictated by these films.

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.

A long life 4 V class lithium-ion polymer battery with liquid-free polymer electrolyte

NASA Astrophysics Data System (ADS)

Kobayashi, Yo; Shono, Kumi; Kobayashi, Takeshi; Ohno, Yasutaka; Tabuchi, Masato; Oka, Yoshihiro; Nakamura, Tatsuya; Miyashiro, Hajime

2017-02-01

Ether-based solid polymer electrolyte (SPE) is one of the most well-known lithium ion conductors. Unlike the other inorganic electrolytes, SPE exhibits advantages of flexibility and large-area production, enabling low cost production of large size batteries. However, because the ether group is oxidized at 4 V versus Li/Li+ cathode, and due to its high irreversibility with the carbon anode, ether-based SPE was believed to be inapplicable to 4 V class lithium-ion batteries with carbon anode. Here we report a remarkably stable SPE in combination with a 4 V class cathode and carbon anode achieved by the proper design at the interface. The introduced boron-based lithium salt prohibits further oxidation of SPE at the cathode interface. The surface modification of graphite by the annealing of polyvinyl chloride mostly prohibits the continuous consumption of lithium at the graphite anode. Using above interface design, we achieved 60% capacity retention after 5400 cycles. The proposed battery provides a possible approach for realizing flammable electrolyte-free lithium-ion batteries, which achieve innovative safety improvements of large format battery systems for stationary use.

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

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

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody

2016-06-15

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10{sup −3} S cm{sup −1}. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providingmore » flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g{sup −1} for standard metallic current collectors and (ii) 99.5 mAh g{sup −1} for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.« less

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

NASA Astrophysics Data System (ADS)

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody; Agarwal, Mangilal

2016-06-01

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10-3 S cm-1. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providing flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g-1 for standard metallic current collectors and (ii) 99.5 mAh g-1 for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.

Ultrashort pulsed laser ablation for decollation of solid state lithium-ion batteries

NASA Astrophysics Data System (ADS)

Hördemann, C.; Anand, H.; Gillner, A.

2017-08-01

Rechargeable lithium-ion batteries with liquid electrolytes are the main energy source for many electronic devices that we use in our everyday lives. However, one of the main drawbacks of this energy storage technology is the use of liquid electrolyte, which can be hazardous to the user as well as the environment. Moreover, lithium-ion batteries are limited in voltage, energy density and operating temperature range. One of the most novel and promising battery technologies available to overcome the above-mentioned drawbacks is the Solid-State Lithium-Ion Battery (SSLB). This battery type can be produced without limitations to the geometry and is also bendable, which is not possible with conventional batteries1 . Additionally, SSLBs are characterized by high volumetric and gravimetric energy density and are intrinsically safe since no liquid electrolyte is used2-4. Nevertheless, the manufacturing costs of these batteries are still high. The existing production-technologies are comparable to the processes used in the semiconductor industry and single cells are produced in batches with masked-deposition at low deposition rates. In order to decrease manufacturing costs and to move towards continuous production, Roll2Roll production methods are being proposed5, 6. These methods offer the possibility of producing large quantities of substrates with deposited SSLB-layers. From this coated substrate, single cells can be cut out. For the flexible decollation of SSLB-cells from the substrate, new manufacturing technologies have to be developed since blade-cutting, punching or conventional laser-cutting processes lead to short circuiting between the layers. Here, ultra-short pulsed laser ablation and cutting allows the flexible decollation of SSLBs. Through selective ablation of individual layers, an area for the cutting kerf is prepared to ensure a shortcut-free decollation.

Calculations of high-power production target and beamdump for the GSI future Super-FRS for a fast extraction scheme at the FAIR Facility

NASA Astrophysics Data System (ADS)

Tahir, N. A.; Weick, H.; Iwase, H.; Geissel, H.; Hoffmann, D. H. H.; Kindler, B.; Lommel, B.; Radon, T.; Münzenberg, G.; Shutov, A.; Sümmerer, K.; Winkler, M.

2005-06-01

A superconducting fragment separator (Super-FRS) is being designed for the production and separation of radioactive isotopes at the future FAIR (Facility for Antiprotons and Ion Research) facility at Darmstadt. This paper discusses various aspects and requirements for the high-power production target that will be used in the Super-FRS experiments. The production target must survive over an extended period of time as it will be used during the course of many experiments. The specific power deposited by the high intensity beam that will be generated at the future FAIR facility will be high enough to destroy the target in most of the cases as a result of a single shot from the new heavy ion synchrotrons SIS100/300. By using an appropriate beam intensity and focal spot parameters, the target would survive after being irradiated once. However, the heat should be dissipated efficiently before the same target area is irradiated again. We have considered a wheel shaped solid carbon target that rotates around its axis so that different areas of the target are irradiated successively. This allows for cooling of the beam heated region by thermal conduction before the same part of the target is irradiated a second time. Another attractive option is to use a liquid jet target at the Super-FRS. First calculations of a possible liquid lithium target are also presented in this paper. One of the advantages of using lithium as a target is that it will survive even if one uses a smaller focal spot, which has half the area of that used for a solid carbon target. This will significantly improve the isotope resolution. A similar problem associated with these experiments will be safe deposition of the beam energy in a beamdump after its interaction with the production target. We also present calculations to study the suitability of a proposed beamdump.

Performance evaluation of a non-woven lithium ion battery separator prepared through a paper-making process

NASA Astrophysics Data System (ADS)

Huang, Xiaosong

2014-06-01

Porous separator functions to electrically insulate the negative and positive electrodes yet communicate lithium ions between the two electrodes when infiltrated with a liquid electrolyte. The separator must fulfill numerous requirements (e.g. permeability, wettability, and thermal stability) in order to optimize the abuse tolerance and electrochemical performance of a battery. Non-woven mat separators have advantages such as high porosity and heat resistance. However, their applications in lithium ion batteries are very limited as their inadequate pore structures could cause accelerated battery performance degradation and even internal short. This work features the development of thermally stable non-woven composite separators using a low cost paper-making process. The composite separators offer significantly improved thermal dimensional stability and exhibit superior wettability by the liquid electrolyte compared to a conventional polypropylene separator. The open porous structures of the non-woven composite separators also resulted in high effective ionic conductivities. The electrochemical performance of the composite separators was tested in coin cells. Stable cycle performances and improved rate capabilities have been observed for the coin cells with these composite separators.

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.

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

Fauzi, Iqbal, E-mail: arcana@chem.itb.ac.id; Arcana, I Made, E-mail: arcana@chem.itb.ac.id

Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the component’s composition respectively on the properties of polymer electrolyte, was carried out by analyzed of it’s characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensilemore » resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 × 10{sup −6} S/cm up to 6.01 × 10{sup −4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 × 10{sup −3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.« less

Solid-State Electrolyte Anchored with a Carboxylated Azo Compound for All-Solid-State Lithium Batteries.

PubMed

Luo, Chao; Ji, Xiao; Chen, Ji; Gaskell, Karen J; He, Xinzi; Liang, Yujia; Jiang, Jianjun; Wang, Chunsheng

2018-05-23

Organic electrode materials are promising for green and sustainable lithium-ion batteries. However, the high solubility of organic materials in the liquid electrolyte results in the shuttle reaction and fast capacity decay. Herein, azo compounds are firstly applied in all-solid-state lithium batteries (ASSLB) to suppress the dissolution challenge. Due to the high compatibility of azobenzene (AB) based compounds to Li 3 PS 4 (LPS) solid electrolyte, the LPS solid electrolyte is used to prevent the dissolution and shuttle reaction of AB. To maintain the low interface resistance during the large volume change upon cycling, a carboxylate group is added into AB to provide 4-(phenylazo) benzoic acid lithium salt (PBALS), which could bond with LPS solid electrolyte via the ionic bonding between oxygen in PBALS and lithium ion in LPS. The ionic bonding between the active material and solid electrolyte stabilizes the contact interface and enables the stable cycle life of PBALS in ASSLB. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Outlook on Lithium Ion Battery Technology

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

Manthiram, Arumugam

Lithium ion batteries as a power source are dominating in portable electronics, penetrating the electric vehicle market, and on the verge of entering the utility market for grid-energy storage. Depending on the application, trade-offs among the various performance parameters—energy, power, cycle life, cost, safety, and environmental impact—are often needed, which are linked to severe materials chemistry challenges. The current lithium ion battery technology is based on insertion-reaction electrodes and organic liquid electrolytes. With an aim to increase the energy density or optimize the other performance parameters, new electrode materials based on both insertion reaction and dominantly conversion reaction along withmore » solid electrolytes and lithium metal anode are being intensively pursued. In conclusion, this article presents an outlook on lithium ion technology by providing first the current status and then the progress and challenges with the ongoing approaches. In light of the formidable challenges with some of the approaches, the article finally points out practically viable near-term strategies.« less

An Outlook on Lithium Ion Battery Technology

DOE PAGES

Manthiram, Arumugam

2017-09-07

Lithium ion batteries as a power source are dominating in portable electronics, penetrating the electric vehicle market, and on the verge of entering the utility market for grid-energy storage. Depending on the application, trade-offs among the various performance parameters—energy, power, cycle life, cost, safety, and environmental impact—are often needed, which are linked to severe materials chemistry challenges. The current lithium ion battery technology is based on insertion-reaction electrodes and organic liquid electrolytes. With an aim to increase the energy density or optimize the other performance parameters, new electrode materials based on both insertion reaction and dominantly conversion reaction along withmore » solid electrolytes and lithium metal anode are being intensively pursued. In conclusion, this article presents an outlook on lithium ion technology by providing first the current status and then the progress and challenges with the ongoing approaches. In light of the formidable challenges with some of the approaches, the article finally points out practically viable near-term strategies.« less

Interfacial behaviours between lithium ion conductors and electrode materials in various battery systems

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

Wu, Bingbin; Wang, Shanyu; Evans IV, Willie J.

In recent years room temperature Li+ ion conductors have been intensively revisited in order to develop safe lithium ion (Li-ion) batteries and beyond that can be deployed in the electrical vehicles. Through careful modification on materials synthesis, promising solid Li+ conductors with high ionic conductivity, competitve with liquid electrolytes, have been demonstrated. However, the integration of those highly conductive solid electrolytes into the whole system is still very challenging mainly due to the high impedance existing in the different interfaces throughout the entire battery structure. Herein , this review paper focuses on the overview of the interfacial behaviors between Li+more » conductors and cathode/anode materials. The origin, evolution and potential solutions to reuce these interfacial impedances are reviewed for various battery systems spanning from Li-ion, lithium sulfur (Li-S), lithium oxygen (Li-O2) batteries to lithium metal protection. The predicted gravimetric and volumetric energy densities at different scenarios are also discussed along with the prospectives for further development of solid state batteries.« less

An Outlook on Lithium Ion Battery Technology

PubMed Central

2017-01-01

Lithium ion batteries as a power source are dominating in portable electronics, penetrating the electric vehicle market, and on the verge of entering the utility market for grid-energy storage. Depending on the application, trade-offs among the various performance parameters—energy, power, cycle life, cost, safety, and environmental impact—are often needed, which are linked to severe materials chemistry challenges. The current lithium ion battery technology is based on insertion-reaction electrodes and organic liquid electrolytes. With an aim to increase the energy density or optimize the other performance parameters, new electrode materials based on both insertion reaction and dominantly conversion reaction along with solid electrolytes and lithium metal anode are being intensively pursued. This article presents an outlook on lithium ion technology by providing first the current status and then the progress and challenges with the ongoing approaches. In light of the formidable challenges with some of the approaches, the article finally points out practically viable near-term strategies. PMID:29104922

Dynamic NMR studies of polymer electrolyte materials for application to lithium-ion batteries and fuel cells

NASA Astrophysics Data System (ADS)

Khalfan, Amish N.

This dissertation investigates the structural and dynamical properties of polymer electrolyte materials for applications to lithium-ion batteries and fuel cells. The nuclear magnetic resonance (NMR) technique was used to characterize these materials. NMR aids in understanding the local environments of nuclei and the mobility of a molecular/ionic species. Five research projects were carried out, and they have been outlined in this work. NASA has developed rod-coil block copolymers for use as electrolytes in lithium-ion batteries. The copolymers exhibit a microphase separation within their structure leading to the formation of ionically conducting channels. We studied ion transport properties of the copolymers, and determined the predominant mechanism for transport to occur in the amorphous phase. Seven gel polymer electrolytes, each containing a mixture of LiBETI salt and organic solvents, were studied. Two of them incorporated BMI (1-n-butyl-3-methylimidazolium) ionic liquid. Ionic liquids are room temperature molten salts. BMI had been thought to enhance ion mobility. However, the BMI component was observed to restrict ion mobility. Gel polymer electrolytes containing LiTFSI salt and P13TFSI ionic liquid with or without the inclusion of ethylene carbonate (EC) were studied for application to lithium metal/air batteries, which have high theoretical energy densities. The addition of EC was found to improve lithium ion transport. The gels with EC therefore prove to be favorable for use as electrolytes in lithium metal/air batteries. Highly sulfonated poly(arylenethioethersulfone) (SPTES) membranes were examined for use in direct methanol fuel cells (DMFCs) as an alternative to the Nafion membrane. DMFCs use methanol as a fuel instead of reformed hydrogen as in conventional proton exchange membrane fuel cells. Compared to Nafion, the SPTES membranes were shown to retain water better at high temperatures and yield lower methanol diffusion. SPTES membranes with the addition of fluorine groups (6F-SPTES) were also studied, and these membranes had been thought to show an improvement in water transport properties over SPTES. However, water diffusion studies of the 6F-SPTES membranes revealed the fluorinated membranes to be unfavorable. The morphology of the FSPTES is suspected to be more susceptible to the loss of bound water at higher temperatures than SPTES.

Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

PubMed Central

Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

2015-01-01

The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm−2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm−2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion). PMID:26411701

Scientific opportunities at SARAF with a liquid lithium jet target neutron source

NASA Astrophysics Data System (ADS)

Silverman, Ido; Arenshtam, Alex; Berkovits, Dan; Eliyahu, Ilan; Gavish, Inbal; Grin, Asher; Halfon, Shlomi; Hass, Michael; Hirsh, T. Y.; Kaizer, Boaz; Kijel, Daniel; Kreisel, Arik; Mardor, Israel; Mishnayot, Yonatan; Palchan, Tala; Perry, Amichay; Paul, Michael; Ron, Guy; Shimel, Guy; Shor, Asher; Tamim, Noam; Tessler, Moshe; Vaintraub, Sergey; Weissman, Leo

2018-05-01

SARAF (Soreq Applied Research Accelerator Facility) is based on a 5 mA, 40 MeV, proton/deuteron accelerator. Phase-I, operational since 2010, provides proton and deuteron beams up to 4 and 5 MeV, respectively, for basic and applied research activities. The high power Liquid-Lithium jet Target (LiLiT), with 1.912 MeV proton beam, provides high flux quasi-Maxwellian neutrons at kT 30 keV (about 2 × 1010 n/s/cm2/mA on the irradiated sample, about 1 cm from the target), enabling studies of s-process reactions relevant to nucleo-synthesis of the heavy elements in giant AGB stars. With higher energy proton beams and with deuterons, LiLiT can provide higher fluxes of high energy neutrons up to 20 MeV. The experimental program with SARAF phase-I will be enhanced shortly with a new target room complex which is under construction. Finally, SARAF phase-II, planned to start operation at 2023, will enable full capabilities with proton/ deuteron beams at 5 mA and 40 MeV. Liquid lithium targets will then be used to produce neutron sources with intensities of 1015 n/s, which after thermalization will provide thermal neutron (25 meV) fluxes of about 1012 n/s/cm2 at the entrance to neutron beam lines to diffraction and radiography stations.

Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

NASA Astrophysics Data System (ADS)

Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

2015-09-01

The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm-2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm-2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion).

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.

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

Pascal, Tod A.; Villaluenga, Irune; Wujcik, Kevin H.

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ~30° below the expectedmore » freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.« less

Vaporization of liquid Pb-Li eutectic alloy from 1000K to 1200K - A high temperature mass spectrometric study

NASA Astrophysics Data System (ADS)

Jain, U.; Mukherjee, A.; Dey, G. K.

2017-09-01

Liquid lead-lithium eutectic will be used as a coolant in fusion reactor blanket loop. Vapor pressure of the eutectic is an important parameter to accurately predict its in-loop behavior. Past measurements of vapor pressure of the eutectic relied on indirect methods. In this paper, we report for the first time the in-situ vaporization behavior of the liquid alloy between 1042 and 1176 K by Knudsen effusion mass spectrometry (KEMS). It was seen that the vaporization occurred by independent evaporation of lead and lithium. No complex intermetallic vapor was seen in the mass spectra. The partial pressures and enthalpy of vaporization of Pb and Li were evaluated directly from the measured ion intensities formed from the equilibrium vapor over the alloy. The activity of Li over a temperature range of 1042-1176 K was found to be 4.8 × 10-5 to that of pure Li, indicating its very low activity in the alloy.

Upgraded flowing liquid lithium limiter for improving Li coverage uniformity and erosion resistance in EAST device

NASA Astrophysics Data System (ADS)

Zuo, G. Z.; Hu, J. S.; Maingi, R.; Yang, Q. X.; Sun, Z.; Huang, M.; Chen, Y.; Yuan, X. L.; Meng, X. C.; Xu, W.; Gentile, C.; Carpe, A.; Diallo, A.; Lunsford, R.; Mansfield, D.; Osborne, T.; Tritz, K.; Li, J. G.

2017-12-01

We report on design and technology improvements for a flowing liquid lithium (FLiLi) limiter inserted into auxiliary heated discharges in the experimental advanced superconducting tokamak device. In order to enhance Li coverage uniformity and erosion resistance, a new liquid Li distributor with homogenous channels was implemented. In addition, two independent electromagnetic pumps and a new horizontal capillary structure contributed to an improvement in the observed Li flow uniformity (from 30% in the previous FLiLi design to >80% in this FLiLi design). To improve limiter surface erosion resistance, hot isostatic press technology was applied, which improved the thermal contact between thin stainless steel protective layers covering the Cu heat sink. The thickness of the stainless steel layer was increased from 0.1 mm to 0.5 mm, which also helped macroscopic erosion resilience. Despite the high auxiliary heating power up to 4.5 MW, no Li bursts were recorded from FLiLi, underscoring the improved performance of this new design.

A model for the Pockels effect in distorted liquid crystal blue phases

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

Castles, F., E-mail: flynn.castles@materials.ox.ac.uk

2015-09-07

Recent experiments have found that a mechanically distorted blue phase can exhibit a primary linear electro-optic (Pockels) effect [F. Castles et al., Nat. Mater. 13, 817 (2014)]. Here, it is shown that flexoelectricity can account for the experimental results and a model, which is based on continuum theory but takes into account the sub-unit-cell structure, is proposed. The model provides a quantitative description of the effect accurate to the nearest order of magnitude and predicts that the Pockels coefficient(s) in an optimally distorted blue phase may be two orders of magnitude larger than in lithium niobate.

Low-Polarization Lithium-Oxygen Battery Using [DEME][TFSI] Ionic Liquid Electrolyte.

PubMed

Ulissi, Ulderico; Elia, Giuseppe Antonio; Jeong, Sangsik; Mueller, Franziska; Reiter, Jakub; Tsiouvaras, Nikolaos; Sun, Yang-Kook; Scrosati, Bruno; Passerini, Stefano; Hassoun, Jusef

2018-01-10

The room-temperature molten salt mixture of N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl) imide ([DEME][TFSI]) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt is herein reported as electrolyte for application in Li-O 2 batteries. The [DEME][TFSI]-LiTFSI solution is studied in terms of ionic conductivity, viscosity, electrochemical stability, and compatibility with lithium metal at 30 °C, 40 °C, and 60 °C. The electrolyte shows suitable properties for application in Li-O 2 battery, allowing a reversible, low-polarization discharge-charge performance with a capacity of about 13 Ah g-1carbon in the positive electrode and coulombic efficiency approaching 100 %. The reversibility of the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) is demonstrated by ex situ XRD and SEM studies. Furthermore, the study of the cycling behavior of the Li-O 2 cell using the [DEME][TFSI]-LiTFSI electrolyte at increasing temperatures (from 30 to 60 °C) evidences enhanced energy efficiency together with morphology changes of the deposited species at the working electrode. In addition, the use of carbon-coated Zn 0.9 Fe 0.1 O (TMO-C) lithium-conversion anode in an ionic-liquid-based Li-ion/oxygen configuration is preliminarily demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Altshuler, Gennady; Manor, Ofer, E-mail: manoro@technion.ac.il

A MHz vibration, or an acoustic wave, propagating in a solid substrate may support the convective spreading of a liquid film. Previous studies uncovered this ability for fully wetting silicon oil films under the excitation of a MHz Rayleigh surface acoustic wave (SAW), propagating in a lithium niobate substrate. Partially wetting de-ionized water films, however, appeared immune to this spreading mechanism. Here, we use both theory and experiment to reconsider this situation and show partially wetting water films may spread under the influence of a propagating MHz vibration. We demonstrate distinct capillary and convective (vibrational/acoustic) spreading regimes that are governedmore » by a balance between convective and capillary mechanisms, manifested in the non-dimensional number θ{sup 3}/We, where θ is the three phase contact angle of the liquid with the solid substrate and We ≡ ρU{sup 2}H/γ; ρ, γ, H, and U are the liquid density, liquid/vapour surface tension, characteristic film thickness, and the characteristic velocity amplitude of the propagating vibration on the solid surface, respectively. Our main finding is that the vibration will support a continuous spreading motion of the liquid film out of a large reservoir if the convective mechanism prevails (θ{sup 3}/We < 1); otherwise (θ{sup 3}/We > 1), the dynamics of the film is governed by the capillary mechanism.« less

Heat pipe dynamic behavior

NASA Technical Reports Server (NTRS)

Issacci, F.; Roche, G. L.; Klein, D. B.; Catton, I.

1988-01-01

The vapor flow in a heat pipe was mathematically modeled and the equations governing the transient behavior of the core were solved numerically. The modeled vapor flow is transient, axisymmetric (or two-dimensional) compressible viscous flow in a closed chamber. The two methods of solution are described. The more promising method failed (a mixed Galerkin finite difference method) whereas a more common finite difference method was successful. Preliminary results are presented showing that multi-dimensional flows need to be treated. A model of the liquid phase of a high temperature heat pipe was developed. The model is intended to be coupled to a vapor phase model for the complete solution of the heat pipe problem. The mathematical equations are formulated consistent with physical processes while allowing a computationally efficient solution. The model simulates time dependent characteristics of concern to the liquid phase including input phase change, output heat fluxes, liquid temperatures, container temperatures, liquid velocities, and liquid pressure. Preliminary results were obtained for two heat pipe startup cases. The heat pipe studied used lithium as the working fluid and an annular wick configuration. Recommendations for implementation based on the results obtained are presented. Experimental studies were initiated using a rectangular heat pipe. Both twin beam laser holography and laser Doppler anemometry were investigated. Preliminary experiments were completed and results are reported.

Diagnosis of power fade mechanisms in high-power lithium-ion cells

NASA Astrophysics Data System (ADS)

Abraham, D. P.; Liu, J.; Chen, C. H.; Hyung, Y. E.; Stoll, M.; Elsen, N.; MacLaren, S.; Twesten, R.; Haasch, R.; Sammann, E.; Petrov, I.; Amine, K.; Henriksen, G.

Hybrid electric vehicles (HEV) need long-lived high-power batteries as energy storage devices. Batteries based on lithium-ion technology can meet the high-power goals but have been unable to meet HEV calendar-life requirements. As part of the US Department of Energy's Advanced Technology Development (ATD) Program, diagnostic studies are being conducted on 18650-type lithium-ion cells that were subjected to accelerated aging tests at temperatures ranging from 40 to 70 °C. This article summarizes data obtained by gas chromatography, liquid chromatography, electron microscopy, X-ray spectroscopy and electrochemical techniques, and identifies cell components that are responsible for the observed impedance rise and power fade.

Liquid lithium target as a high intensity, high energy neutron source

DOEpatents

Parkin, Don M.; Dudey, Norman D.

1976-01-01

This invention provides a target jet for charged particles. In one embodiment the charged particles are high energy deuterons that bombard the target jet to produce high intensity, high energy neutrons. To this end, deuterons in a vacuum container bombard an endlessly circulating, free-falling, sheet-shaped, copiously flowing, liquid lithium jet that gushes by gravity from a rectangular cross-section vent on the inside of the container means to form a moving web in contact with the inside wall of the vacuum container. The neutrons are produced via break-up of the beam in the target by stripping, spallation and compound nuclear reactions in which the projectiles (deuterons) interact with the target (Li) to produce excited nuclei, which then "boil off" or evaporate a neutron.

Developing the Pulsed Fission-Fusion (PuFF) Engine

NASA Technical Reports Server (NTRS)

Adams, Robert B.; Cassibry, Jason; Bradley, David; Fabisinski, Leo; Statham, Geoffrey

2014-01-01

In September 2013 the NASA Innovative Advanced Concept (NIAC) organization awarded a phase I contract to the PuFF team. Our phase 1 proposal researched a pulsed fission-fusion propulsion system that compressed a target of deuterium (D) and tritium (T) as a mixture in a column, surrounded concentrically by Uranium. The target is surrounded by liquid lithium. A high power current would flow down the liquid lithium and the resulting Lorentz force would compress the column by roughly a factor of 10. The compressed column would reach criticality and a combination of fission and fusion reactions would occur. Our Phase I results, summarized herein, review our estimates of engine and vehicle performance, our work to date to model the fission-fusion reaction, and our initial efforts in experimental analysis.

Solid-liquid phase coexistence of alkali nitrates from molecular dynamics simulations.

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

Jayaraman, Saivenkataraman

2010-03-01

Alkali nitrate eutectic mixtures are finding application as industrial heat transfer fluids in concentrated solar power generation systems. An important property for such applications is the melting point, or phase coexistence temperature. We have computed melting points for lithium, sodium and potassium nitrate from molecular dynamics simulations using a recently developed method, which uses thermodynamic integration to compute the free energy difference between the solid and liquid phases. The computed melting point for NaNO3 was within 15K of its experimental value, while for LiNO3 and KNO3, the computed melting points were within 100K of the experimental values [4]. We aremore » currently extending the approach to calculate melting temperatures for binary mixtures of lithium and sodium nitrate.« less

High voltage stable liquid electrolytes for Li 1+ xMn 2O 4/carbon rocking-chair lithium batteries

NASA Astrophysics Data System (ADS)

Guyomard, D.; Tarascon, J. M.

A high voltage oxidation-resistant electrolyte is required for Li 1+ xMn 2O 4/carbon rocking-chair cells that need to be charged up to a voltage higher than 4.3 V. Many electrolyte compositions have been tested for their ability to resist to high voltages on Li 1+ xMn 2O 4 electrodes and their ability to maintain high ionic conductivity in a wide temperature range. This survey allowed us to select new electrolyte compositions in the system dimethyl carbonate (DMC) + ethylene carbonate (EC) + lithium hexafluorophosphate (LiPF 6) that are kinetically stable up to almost 5 V versus lithium at 55 °C on Li 1+ xMn 2O 4 electrodes. Low rate potentiostatic experiments, coupled with coulombmetric measurements in the 4.25-5.1 V range, allowed to select the following compositions: (DMC + EC) (1:2) + 1 M LiPF 6 and (DMC + EC) (2:1) + 1.5 M LiPF 6 as the best. These compositions have been used in practical Li 1+ xMn 2O 4/carbon rocking-chair batteries and show better performance in terms of cycle life and self-discharge over a wider temperature range. They are compatible with rocking-chair batteries based on LiCoO 2 and LiNiO 2 as well.

Compatibility of lithium plasma-facing surfaces with high edge temperatures in the Lithium Tokamak Experiment

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

Majeski, R.; Bell, R. E.; Boyle, D. P.

We measured high edge electron temperatures (200 eV or greater) at the wall-limited plasma boundary in the Lithium Tokamak Experiment (LTX). Flat electron temperature profiles are a long-predicted consequence of low recycling boundary conditions. Plasma density in the outer scrape-off layer is very low, 2-3 x 10(17) m(-3), consistent with a low recycling metallic lithium boundary. In spite of the high edge temperature, the core impurity content is low. Z(eff) is estimated to be similar to 1.2, with a very modest contribution (< 0.1) from lithium. Experiments are transient. Gas puffing is used to increase the plasma density. After gasmore » injection stops, the discharge density is allowed to drop, and the edge is pumped by the low recycling lithium wall. An upgrade to LTX-LTX-beta, which includes a 35A, 20 kV neutral beam injector (on loan to LTX from Tri-Alpha Energy) to provide core fueling to maintain constant density, as well as auxiliary heating, is underway. LTX-beta is briefly described.« less

Compatibility of lithium plasma-facing surfaces with high edge temperatures in the Lithium Tokamak Experiment

DOE PAGES

Majeski, R.; Bell, R. E.; Boyle, D. P.; ...

2017-03-20

We measured high edge electron temperatures (200 eV or greater) at the wall-limited plasma boundary in the Lithium Tokamak Experiment (LTX). Flat electron temperature profiles are a long-predicted consequence of low recycling boundary conditions. Plasma density in the outer scrape-off layer is very low, 2-3 x 10(17) m(-3), consistent with a low recycling metallic lithium boundary. In spite of the high edge temperature, the core impurity content is low. Z(eff) is estimated to be similar to 1.2, with a very modest contribution (< 0.1) from lithium. Experiments are transient. Gas puffing is used to increase the plasma density. After gasmore » injection stops, the discharge density is allowed to drop, and the edge is pumped by the low recycling lithium wall. An upgrade to LTX-LTX-beta, which includes a 35A, 20 kV neutral beam injector (on loan to LTX from Tri-Alpha Energy) to provide core fueling to maintain constant density, as well as auxiliary heating, is underway. LTX-beta is briefly described.« less

Compatibility of lithium plasma-facing surfaces with high edge temperatures in the Lithium Tokamak Experiment

NASA Astrophysics Data System (ADS)

Majeski, R.; Bell, R. E.; Boyle, D. P.; Kaita, R.; Kozub, T.; LeBlanc, B. P.; Lucia, M.; Maingi, R.; Merino, E.; Raitses, Y.; Schmitt, J. C.; Allain, J. P.; Bedoya, F.; Bialek, J.; Biewer, T. M.; Canik, J. M.; Buzi, L.; Koel, B. E.; Patino, M. I.; Capece, A. M.; Hansen, C.; Jarboe, T.; Kubota, S.; Peebles, W. A.; Tritz, K.

2017-05-01

High edge electron temperatures (200 eV or greater) have been measured at the wall-limited plasma boundary in the Lithium Tokamak Experiment (LTX). Flat electron temperature profiles are a long-predicted consequence of low recycling boundary conditions. Plasma density in the outer scrape-off layer is very low, 2-3 × 1017 m-3, consistent with a low recycling metallic lithium boundary. Despite the high edge temperature, the core impurity content is low. Zeff is estimated to be ˜1.2, with a very modest contribution (<0.1) from lithium. Experiments are transient. Gas puffing is used to increase the plasma density. After gas injection stops, the discharge density is allowed to drop, and the edge is pumped by the low recycling lithium wall. An upgrade to LTX-LTX-β, which includes a 35A, 20 kV neutral beam injector (on loan to LTX from Tri-Alpha Energy) to provide core fueling to maintain constant density, as well as auxiliary heating, is underway. LTX-β is briefly described.

Use of liquid metals in nuclear and thermonuclear engineering, and in other innovative technologies

NASA Astrophysics Data System (ADS)

Rachkov, V. I.; Arnol'dov, M. N.; Efanov, A. D.; Kalyakin, S. G.; Kozlov, F. A.; Loginov, N. I.; Orlov, Yu. I.; Sorokin, A. P.

2014-05-01

By now, a good deal of experience has been gained with using liquid metals as coolants in nuclear power installations; extensive knowledge has been gained about the physical, thermophysical, and physicochemical properties of these coolants; and the scientific principles and a set of methods and means for handling liquid metals as coolants for nuclear power installations have been elaborated. Prototype and commercialgrade sodium-cooled NPP power units have been developed, including the BOR-60, BN-350, and BN-600 power units (the Soviet Union); the Rapsodie, Phenix, and Superphenix power units (France), the EBR-II power unit (the United States); and the PFR power unit (the United Kingdom). In Russia, dedicated nuclear power installations have been constructed, including those with a lead-bismuth coolant for nuclear submarines and with sodium-potassium alloy for spacecraft (the Buk and Topol installations), which have no analogs around the world. Liquid metals (primarily lithium and its alloy with lead) hold promise for use in thermonuclear power engineering, where they can serve not only as a coolant, but also as tritium-producing medium. In this article, the physicochemical properties of liquid metal coolants, as well as practical experience gained from using them in nuclear and thermonuclear power engineering and in innovative technologies are considered, and the lines of further research works are formulated. New results obtained from investigations carried out on the Pb-Bi and Pb for the SVBR and BREST fast-neutron reactors (referred to henceforth as fast reactors) and for controlled accelerator systems are described.

Aftereffects of Lithium-Conditioned Stimuli on Consummatory Behavior

ERIC Educational Resources Information Center

Domjan, Michael; Gillan, Douglas J.

1977-01-01

To complement investigations of the direct effects of lithium toxicosis on consummatory behavior, these experiments were designed to determine the aftereffects on drinking of exposure to a conditioned stimulus previously paired with lithium. (Author/RK)

Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries

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

Sun Liang; Key Laboratory of Resources Chemistry of Nonferrous Metals, Central South University, Ministry of Education of the People's Republic of China; Qiu Keqiang, E-mail: qiuwhs@sohu.com

2012-08-15

Graphical abstract: Display Omitted Highlights: Black-Right-Pointing-Pointer Vacuum pyrolysis as a pretreatment was used to separate cathode material from aluminum foils. Black-Right-Pointing-Pointer Cobalt and lithium can be leached using oxalate while cobalt can be directly precipitated as cobalt oxalate. Black-Right-Pointing-Pointer Cobalt and lithium can be separated efficiently from each other only in the oxalate leaching process. Black-Right-Pointing-Pointer High reaction efficiency of LiCoO{sub 2} was obtained with oxalate. - Abstract: Spent lithium-ion batteries containing lots of strategic resources such as cobalt and lithium are considered as an attractive secondary resource. In this work, an environmentally compatible process based on vacuum pyrolysis, oxalatemore » leaching and precipitation is applied to recover cobalt and lithium from spent lithium-ion batteries. Oxalate is introduced as leaching reagent meanwhile as precipitant which leaches and precipitates cobalt from LiCoO{sub 2} and CoO directly as CoC{sub 2}O{sub 4}{center_dot}2H{sub 2}O with 1.0 M oxalate solution at 80 Degree-Sign C and solid/liquid ratio of 50 g L{sup -1} for 120 min. The reaction efficiency of more than 98% of LiCoO{sub 2} can be achieved and cobalt and lithium can also be separated efficiently during the hydrometallurgical process. The combined process is simple and adequate for the recovery of valuable metals from spent lithium-ion batteries.« less

Recovery of lithium and cobalt from spent lithium-ion batteries using organic acids: Process optimization and kinetic aspects.

PubMed

Golmohammadzadeh, Rabeeh; Rashchi, Fereshteh; Vahidi, Ehsan

2017-06-01

An environmentally-friendly route based on hydrometallurgy was investigated for the recovery of cobalt and lithium from spent lithium ion batteries (LIBs) using different organic acids (citric acid, Dl-malic acid, oxalic acid and acetic acid). In this investigation, response surface methodology (RSM) was utilized to optimize leaching parameters including solid to liquid ratio (S/L), temperature, acid concentration, type of organic acid and hydrogen peroxide concentration. Based on the results obtained from optimizing procedure, temperature was recognized as the most influential parameter. In addition, while 81% of cobalt was recovered, the maximum lithium recovery of 92% was achieved at the optimum leaching condition of 60°C, S/L: 30gL -1 , citric acid concentration: 2M, hydrogen peroxide concentration: 1.25Vol.% and leaching time: 2h. Furthermore, results displayed that ultrasonic agitation will enhance the recovery of lithium and cobalt. It was found that the kinetics of cobalt leaching is controlled by surface chemical reaction at temperatures lower than 45°C. However, diffusion through the product layer at temperatures higher than 45°C controls the rate of cobalt leaching. Rate of lithium reaction is controlled by diffusion through the product layer at all the temperatures studied. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synergistic gelation of silica nanoparticles and a sorbitol-based molecular gelator to yield highly-conductive free-standing gel electrolytes.

PubMed

Basrur, Veidhes R; Guo, Juchen; Wang, Chunsheng; Raghavan, Srinivasa R

2013-01-23

Lithium-ion batteries have emerged as the preferred type of rechargeable batteries, but there is a need to improve the performance of the electrolytes therein. Specifically, the challenge is to obtain electrolytes with the mechanical rigidity of solids but with liquid-like conductivities. In this study, we report a class of nanostructured gels that are able to offer this unique combination of properties. The gels are prepared by utilizing the synergistic interactions between a molecular gelator, 1,3:2,4-di-O-methyl-benzylidene-d-sorbitol (MDBS), and a nanoscale particulate material, fumed silica (FS). When MDBS and FS are combined in a liquid consisting of propylene carbonate with dissolved lithium perchlorate salt, the liquid electrolyte is converted into a free-standing gel due to the formation of a strong MDBS-FS network. The gels exhibit elastic shear moduli around 1000 kPa and yield stresses around 11 kPa-both values considerably exceed those obtainable by MDBS or FS alone in the same liquid. At the same time, the gel also exhibits electrochemical properties comparable to the parent liquid, including a high ionic conductivity (~5 × 10(-3) S/cm at room temperature) and a wide electrochemical stability window (up to 4.5 V).

Floating growth of large-scale freestanding TiO2 nanorod films at the gas-liquid interface for additive-free Li-ion battery applications.

PubMed

Xia, Hua-Rong; Li, Jia; Peng, Chen; Sun, Wen-Tao; Li, Long-Wei; Peng, Lian-Mao

2014-10-22

The floating growth process of large-scale freestanding TiO2 nanorod films at the gas-liquid interface was investigated. On the basis of the experiments, a self-templated growth scenario was developed to account for the self-assembly process. In the scenario, titanium complexes function not only as the Ti source for the growth of TiO2 but also as a soft template provider for the floating growth. According to the scenario, several new recipes of preparing freestanding TiO2 nanorod films at the gas-liquid interface were developed. The freestanding film was applied to a lithium ion battery as a binder-free and conducting agent-free anode, and good cyclability was obtained. This work may pave a new way to floating and freestanding TiO2 and other semiconductor materials, which has great potential not only in basic science but also in the applications such as materials engineering, Li-ion battery, photocatalyst, dye-sensitized solar cell, and flexible electronics.

Status of lithium-filled specimen subcapsules for the HFIR-MFE-RB10J experiment

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

Robertson, J.P.; Howell, M.; Lenox, K.E.

1998-09-01

The HFIR-MFE-RB-10J experiment will be irradiated in a Removable Beryllium position in the HFIR for 10 reactor cycles, accumulating approximately 5 dpa in steel. The upper region of the capsule contains two lithium-filled subcapsules containing vanadium specimens. This report describes the techniques developed to achieve a satisfactory lithium fill with a specimen occupancy of 26% in each subcapsule.

Confined Sulfur in 3 D MXene/Reduced Graphene Oxide Hybrid Nanosheets for Lithium-Sulfur Battery.

PubMed

Bao, Weizhai; Xie, Xiuqiang; Xu, Jing; Guo, Xin; Song, Jianjun; Wu, Wenjian; Su, Dawei; Wang, Guoxiu

2017-09-12

Three-dimensional metal carbide MXene/reduced graphene oxide hybrid nanosheets are prepared and applied as a cathode host material for lithium-sulfur batteries. The composite cathodes are obtained through a facile and effective two-step liquid-phase impregnation method. Owing to the unique 3 D layer structure and functional 2 D surfaces of MXene and reduced graphene oxide nanosheets for effective trapping of sulfur and lithium polysulfides, the MXene/reduced graphene oxide/sulfur composite cathodes deliver a high initial capacity of 1144.2 mAh g -1 at 0.5 C and a high level of capacity retention of 878.4 mAh g -1 after 300 cycles. It is demonstrated that hybrid metal carbide MXene/reduced graphene oxide nanosheets could be a promising cathode host material for lithium-sulfur batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

PubMed

Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

2016-01-11

The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Increase of glucocorticoids is not required for the acquisition, but hinders the extinction, of lithium-induced conditioned taste aversion.

PubMed

Kim, Kyu-Nam; Kim, Bom-Taeck; Kim, Young-Sang; Lee, Jong-Ho; Jahng, Jeong Won

2014-05-05

Lithium chloride at doses sufficient to induce conditioned taste aversion (CTA) causes c-Fos expression in the paraventricular nucleus and increases the plasma level of corticosterone with activation of the hypothalamic-pituitary-adrenal axis. This study was conducted to define the role of glucocorticoid in the acquisition and extinction of lithium-induced CTA. In experiment 1, Sprague-Dawley rats received dexamethasone (2mg/kg) or RU486 (20mg/kg) immediately after 5% sucrose access, and then an intraperitoneal injection of isotonic lithium chloride (12ml/kg) was followed with 30min interval. Rats had either 1 or 7 days of recovery period before the daily sucrose drinking tests. In experiment 2, rats were conditioned with the sucrose-lithium pairing, and then received dexamethasone or vehicle at 30min before each drinking test. In experiment 3, adrenalectomized (ADX or ADX+B) rats were subjected to sucrose drinking tests after the sucrose-lithium pairing. Dexamethasone, but not RU486, pretreatment blunted the formation of lithium-induced CTA memory. Dexamethasone prior to each drinking test suppressed sucrose consumption and prolonged the extinction of lithium-induced CTA. Sucrose consumption was significantly suppressed not only in ADX+B rats but also in ADX rats during the first drinking session; however, a significant decrease was found only in ADX rats on the fourth drinking session. These results reveal that glucocorticoid is not a necessary component in the acquisition, but an important player in the extinction, of lithium-induced CTA, and suggest that a pulse increase of glucocorticoid may hinder the extinction memory formation of lithium-induced CTA. Copyright © 2014 Elsevier B.V. All rights reserved.

Pb17Li and lithium: A thermodynamic rationalisation of their radically different chemistry

NASA Astrophysics Data System (ADS)

Hubberstey, Peter

1997-08-01

The contrasting chemistry of Pb17Li and lithium is attributed to their lithium activities. PbLi alloys exhibit marked negative deviations from ideality owing to 'chemical short range order', giving γ Li = 7.26 × 10 -4, aLi = 1.23 × 10 -4 and overlineGLi = -57.8 kJ mol -1 in Pb-17Li at 773 K. This overlineGLi value is sufficiently negative to prevent the reaction of Pb17Li with gaseous hydrogen and nitrogen to form LiH and Li 3N but not with oxygen containing gases to form Li 2O. Similarly, nitride and carbide ceramics are compatible with Pb-17Li but oxide ceramics are liable to degradation. In contrast, unit activity liquid lithium reacts with all the gases and, depending on their free energy of formation, some of the ceramics. Wherea, dissolved oxygen is corrosive in Pb-17Li, giving LiCrO 2, dissolved nitrogen adopts the corrosive role in lithium giving Li 9CrN 5. The instability of LiH in Pb-17Li renders tritium extraction facile; this contrasts with lithium for which tritium extraction is difficult owing to LiH formation.

Vanadium—lithium in-pile loop for comprehensive tests of vanadium alloys and multipurpose coatings

NASA Astrophysics Data System (ADS)

Lyublinski, I. E.; Evtikhin, V. A.; Ivanov, V. B.; Kazakov, V. A.; Korjavin, V. M.; Markovchev, V. K.; Melder, R. R.; Revyakin, Y. L.; Shpolyanskiy, V. N.

1996-10-01

The reliable information on design and material properties of self-cooled Li sbnd Li blanket and liquid metal divertor under neutron radiation conditions can be obtained using the concept of combined technological and material in-pile tests in a vanadium—lithium loop. The method of in-pile loop tests includes studies of vanadium—base alloys resistance, weld resistance under mechanical stress, multipurpose coating formation processes and coatings' resistance under the following conditions: high temperature (600-700°C), lithium velocities up to 10 m/s, lithium with controlled concentration of impurities and technological additions, a neutron load of 0.4-0.5 MW/m 2 and level of irradiation doses up to 5 dpa. The design of such an in-pile loop is considered. The experimental data on corrosion and compatibility with lithium, mechanical properties and welding technology of the vanadium alloys, methods of coatings formation and its radiation tests in lithium environment in the BOR-60 reactor (fast neutron fluence up to 10 26 m -2, irradiation temperature range of 500-523°C) are presented and analyzed as a basis for such loop development.

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.

Liquid electrolytes for lithium and lithium-ion batteries

NASA Astrophysics Data System (ADS)

Blomgren, George E.

A number of advances in electrolytes have occurred in the past 4 years, which have contributed to increased safety, wider temperature range of operation, better cycling and other enhancements to lithium-ion batteries. The changes to basic electrolyte solutions that have occurred to accomplish these advances are discussed in detail. The solvent components that have led to better low-temperature operation are also considered. Also, additives that have resulted in better structure of the solid electrolyte interphase (SEI) are presented as well as proposed methods of operation of these additives. Other additives that have lessened the flammability of the electrolyte when exposed to air and also caused lowering of the heat of reaction with the oxidized positive electrode are discussed. Finally, additives that act to open current-interrupter devices by releasing a gas under overcharge conditions and those that act to cycle between electrodes to alleviate overcharging are presented. As a class, these new electrolytes are often called "functional electrolytes". Possibilities for further progress in this most important area are presented. Another area of active work in the recent past has been the reemergence of ambient-temperature molten salt electrolytes applied to alkali metal and lithium-ion batteries. This revival of an older field is due to the discovery of new salt types that have a higher voltage window (particularly to positive potentials) and also have greatly increased hydrolytic stability compared to previous ionic liquids. While practical batteries have not yet emerged from these studies, the increase in the number of active researchers and publications in the area demonstrates the interest and potentialities of the field. Progress in the field is briefly reviewed. Finally, recent results on the mechanisms for capacity loss on shelf and cycling in lithium-ion cells are reviewed. Progress towards further market penetration by lithium-ion cells hinges on improved understanding of the failure mechanisms of the cells, so that crucial problems can be addressed.

Liquid Silicon Pouch Anode

DTIC Science & Technology

2017-09-06

discharge from cell 10A shown in FIG. 1, as electrons are utilized from negative electrode 28, lithium ions in anolyte 24 travel across membrane 14 to join...Docket No. 300139 11 of 13 [0029] As cell 10B shown in FIG. 2 is charged, lithium ions in catholyte 16 travel across membrane 14. Discharge of these...with a cell 10B’ in a discharged state. Reservoir 32B contracts as anolyte 24 reduces in volume while cell is discharging. Anolyte 24 travels from

Electrochemical Performance of Highly Mesoporous Nitrogen Doped Carbon Cathode in Lithium-Oxygen Batteries (Postprint)

DTIC Science & Technology

2011-03-01

concentrations. Cathode capacity approaching 000mAhg−1 for a Mn based catalyst [7] and cathode capac- ty 5360mAhg−1 for cell employing a hydrophobic ionic ... liquid nd lithium salt were reported [8]. A gravimetric capacity of 813mAhg−1 was achieved using a novel lithium–oxygen cath- de architecture without...andNafion (tetrafluoroethy- ene based fluoropolymer-copolymer) solution in one case and -KB and Nafion in another were prepared and spread on graphite

Quantitative Phase Microscopy for Accurate Characterization of Microlens Arrays

NASA Astrophysics Data System (ADS)

Grilli, Simonetta; Miccio, Lisa; Merola, Francesco; Finizio, Andrea; Paturzo, Melania; Coppola, Sara; Vespini, Veronica; Ferraro, Pietro

Microlens arrays are of fundamental importance in a wide variety of applications in optics and photonics. This chapter deals with an accurate digital holography-based characterization of both liquid and polymeric microlenses fabricated by an innovative pyro-electrowetting process. The actuation of liquid and polymeric films is obtained through the use of pyroelectric charges generated into polar dielectric lithium niobate crystals.

Novel Polyimide Battery Separator Imbibed with Room-Temperature Ionic Liquids

NASA Technical Reports Server (NTRS)

Viggiano, Rocco; Nguyen, Baochau; Wu, James; Dai, Liming; Meador, Mary Ann

2017-01-01

The journey to Mars will require advancements in many existing technologies, including space power and energy storage systems. According to the 2015 NASA Technology Roadmaps, energy storage is a critical technology area to develop for both terrestrial as well as future long-term space missions. Currently, batteries represent one of the major areas in need of advancement, both in terms of energy density as well as safety. Recently, concerns regarding the fire safety of commercial lithium-ion batteries have prompted efforts to produce nonflammable battery components, namely the electrolyte and separator. Commercial lithium-ion batteries utilize polyolefin separators imbibed with a lithium salt dissolved in cyclic carbonates. This separator/electrolyte combination imparts good ionic conductivities in the range of 10(exp -2) to 10(exp -3) S/cm. However, the cyclic carbonates and polyolefin separator are inherently flammable. Room-temperature ionic liquids (RTILs) appear to be a safer alternative to cyclic carbonates. They offer good ionic conductivities, similar to those observed in cyclic carbonates, but are inherently nonvolatile and nonflammable giving them a safety advantage. Many promising RTILs for battery electrolytes are not compatible with commercial polyolefin separator materials. Polyimide aerogels possess an open-porous, fibrillar network architecture which offers a high degree of porosity (typically greater than 85 porous), required for lithium ion conduction, as well as good mechanical properties. Furthermore, these materials are compatible with all tested RTILs. By creating a polyimide gel and imbibing the gel with a RTIL containing a lithium salt instead of super critically drying them to form aerogels, a nonflammable separator/electrolyte system with conductivities in the range of 1x10(exp -3) S/cm has been demonstrated.

Separation and transport of lithium of 10(-5) M in the presence of sodium chloride higher than 0.1 M by 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin.

PubMed

Sun, H; Tabata, M

1999-07-01

A water-soluble porphyrin (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H(2)(obtpps)(4-), H(2)P(4-)) synthesized in our laboratory was applied to a solvent extraction method and a liquid membrane transport of lithium as low as 10(-5) M (M=mol dm(-3)) in the presence of sodium chloride higher than 0.1 M. The lithium porphyrin with five negative charges was extracted successfully into chloroform with tetrabutylammonium ion (But(4)N(+)) at pH 12.7. The extraction constant for the reaction of [LiP(5-)](a)+5[But(4)N](+)(a)right harpoon over left harpoon[(But(4)N)(5)LiP](o) was found to be (1.9+/-0.3)x10(18) M(-5), where the subscripts a and o denote chemical species in aqueous and organic phases, respectively. Lithium was transported to an aqueous phase at pH 7 through a chloroform liquid membrane containing [(But(4)N)(5)HP]. The extraction and transport mechanism was discussed on the basis of extraction constants, chemical species and transportation rate. Lithium in sea water or serum sample was separated and its concentration was determined spectrophotometrically by the present method without any interference from sodium chloride. The interference from transition and heavy metal ions was masked by Mg-EDTA. A calibration curve was linear over a range of 2x10(-6) to 2x10(-5) M at a precision of 1.51% (RSD).

Taste aversion learning produced by combined treatment with subthreshold radiation and lithium chloride

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

Rabin, B.M.; Hunt, W.A.; Lee, J.

1987-08-01

These experiments were designed to determine whether treatment with two subthreshold doses of radiation or lithium chloride, either alone or in combination, could lead to taste aversion learning. The first experiment determined the thresholds for a radiation-induced taste aversion at 15-20 rad and for lithium chloride at 0.30-0.45 mEq/kg. In the second experiment it was shown that exposing rats to two doses of 15 rad separated by up to 3 hr produced a taste aversion. Treatment with two injections of lithium chloride (0.30 mEq/kg) did not produce a significant reduction in preference. Combined treatment with radiation and lithium chloride didmore » produce a taste aversion when the two treatments were administered within 1 hr of each other. The results are discussed in terms of the implications of these findings for understanding the nature of the unconditioned stimuli leading to the acquisition of a conditioned taste aversion.« less

Taste aversion learning produced by combined treatment with subthreshold radiation and lithium chloride.

PubMed

Rabin, B M; Hunt, W A; Lee, J

1987-08-01

These experiments were designed to determine whether treatment with two subthreshold doses of radiation or lithium chloride, either alone or in combination, could lead to taste aversion learning. The first experiment determined the thresholds for a radiation-induced taste aversion at 15-20 rad and for lithium chloride at 0.30-0.45 mEq/kg. In the second experiment it was shown that exposing rats to two doses of 15 rad separated by up to 3 hr produced a taste aversion. Treatment with two injections of lithium chloride (0.30 mEq/kg) did not produce a significant reduction in preference. Combined treatment with radiation and lithium chloride did produce a taste aversion when the two treatments were administered within 1 hr of each other. The results are discussed in terms of the implications of these findings for understanding the nature of the unconditioned stimuli leading to the acquisition of a conditioned taste aversion.

Lithium-antimony-lead liquid metal battery for grid-level energy storage

NASA Astrophysics Data System (ADS)

Wang, Kangli; Jiang, Kai; Chung, Brice; Ouchi, Takanari; Burke, Paul J.; Boysen, Dane A.; Bradwell, David J.; Kim, Hojong; Muecke, Ulrich; Sadoway, Donald R.

2014-10-01

The ability to store energy on the electric grid would greatly improve its efficiency and reliability while enabling the integration of intermittent renewable energy technologies (such as wind and solar) into baseload supply. Batteries have long been considered strong candidate solutions owing to their small spatial footprint, mechanical simplicity and flexibility in siting. However, the barrier to widespread adoption of batteries is their high cost. Here we describe a lithium-antimony-lead liquid metal battery that potentially meets the performance specifications for stationary energy storage applications. This Li||Sb-Pb battery comprises a liquid lithium negative electrode, a molten salt electrolyte, and a liquid antimony-lead alloy positive electrode, which self-segregate by density into three distinct layers owing to the immiscibility of the contiguous salt and metal phases. The all-liquid construction confers the advantages of higher current density, longer cycle life and simpler manufacturing of large-scale storage systems (because no membranes or separators are involved) relative to those of conventional batteries. At charge-discharge current densities of 275 milliamperes per square centimetre, the cells cycled at 450 degrees Celsius with 98 per cent Coulombic efficiency and 73 per cent round-trip energy efficiency. To provide evidence of their high power capability, the cells were discharged and charged at current densities as high as 1,000 milliamperes per square centimetre. Measured capacity loss after operation for 1,800 hours (more than 450 charge-discharge cycles at 100 per cent depth of discharge) projects retention of over 85 per cent of initial capacity after ten years of daily cycling. Our results demonstrate that alloying a high-melting-point, high-voltage metal (antimony) with a low-melting-point, low-cost metal (lead) advantageously decreases the operating temperature while maintaining a high cell voltage. Apart from the fact that this finding puts us on a desirable cost trajectory, this approach may well be more broadly applicable to other battery chemistries.

A study of thermal hydraulic and kinetic phenomena in HYLIFE-2: An inertial confinement fusion reactor

NASA Astrophysics Data System (ADS)

Chen, Xiang Ming

1993-01-01

Researchers have studied the different aspects of commercial fusion energy for several decades. A variety of inertial confinement fusion (ICF) reactors have been proposed. Different from the magnetic confinement fusion concept, inertial confinement fusion does not need long-term confinement of the fusion fuel but achieves fusion reaction in a short microexplosion under a high density, high temperature condition. The HYLIFE-2 reactor design started in 1987 is based on the study of a previous concept called HYLIFE (High Yield Lithium Injection Fusion Energy). Similar to the old concept, the HYLIFE-2 design uses a vacuum chamber in which D-T fusion pellets are injected and ignited by high energy beams shot into the reactor through different ports. The reactor vessel is protected from explosion radiations by a liquid fall (blanket) that also breeds tritium through the (n, alpha) reaction of lithium and conveys the fusion energy to the power cycle. In addition to some geometric chances, the new design replaces liquid metal lithium with the molten salt Flibe (Li2BeF4) as the protective blanket material. The objective was to remove the possibility of fire hazard. The important thermal hydraulic issues in the design are (1) equation of state of Flibe; (2) liquid relaxation after isochoric (constant volume) heating; (3) ablation and gas dynamics; (4) interaction of the vapor and liquid; and (5) condensation of the vaporized material. The first four issues have to do with the internal relaxation after the fusion microexplosion in the chamber. Vaporized material, as well as liquid, may assert strong impulses on the chamber wall during the process of relaxing after absorbing the energy from the microexplosion. Item (5) is related to the rapid vacuum recovery between the ignitions. Some aspects of the first four issues are studied.

Lithium-antimony-lead liquid metal battery for grid-level energy storage.

PubMed

Wang, Kangli; Jiang, Kai; Chung, Brice; Ouchi, Takanari; Burke, Paul J; Boysen, Dane A; Bradwell, David J; Kim, Hojong; Muecke, Ulrich; Sadoway, Donald R

2014-10-16

The ability to store energy on the electric grid would greatly improve its efficiency and reliability while enabling the integration of intermittent renewable energy technologies (such as wind and solar) into baseload supply. Batteries have long been considered strong candidate solutions owing to their small spatial footprint, mechanical simplicity and flexibility in siting. However, the barrier to widespread adoption of batteries is their high cost. Here we describe a lithium-antimony-lead liquid metal battery that potentially meets the performance specifications for stationary energy storage applications. This Li||Sb-Pb battery comprises a liquid lithium negative electrode, a molten salt electrolyte, and a liquid antimony-lead alloy positive electrode, which self-segregate by density into three distinct layers owing to the immiscibility of the contiguous salt and metal phases. The all-liquid construction confers the advantages of higher current density, longer cycle life and simpler manufacturing of large-scale storage systems (because no membranes or separators are involved) relative to those of conventional batteries. At charge-discharge current densities of 275 milliamperes per square centimetre, the cells cycled at 450 degrees Celsius with 98 per cent Coulombic efficiency and 73 per cent round-trip energy efficiency. To provide evidence of their high power capability, the cells were discharged and charged at current densities as high as 1,000 milliamperes per square centimetre. Measured capacity loss after operation for 1,800 hours (more than 450 charge-discharge cycles at 100 per cent depth of discharge) projects retention of over 85 per cent of initial capacity after ten years of daily cycling. Our results demonstrate that alloying a high-melting-point, high-voltage metal (antimony) with a low-melting-point, low-cost metal (lead) advantageously decreases the operating temperature while maintaining a high cell voltage. Apart from the fact that this finding puts us on a desirable cost trajectory, this approach may well be more broadly applicable to other battery chemistries.

First Principles Modeling of Structure and Transport in Solid Polymer Electrolytes, Ionic Liquids, and Methanol/Water Mixtures

DTIC Science & Technology

2016-02-10

potential in making high- performance solid state lithium ion batteries [1,2]. Among them, the polyethylene oxide-alkali salts systems PEO6:XPF6 (X = H...electrolytes for magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group...magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group of Prof. Vito Di

Fabricating solid carbon porous electrodes from powders

DOEpatents

Kaschmitter, James L.; Tran, Tri D.; Feikert, John H.; Mayer, Steven T.

1997-01-01

Fabrication of conductive solid porous carbon electrodes for use in batteries, double layer capacitors, fuel cells, capacitive dionization, and waste treatment. Electrodes fabricated from low surface area (<50 m.sup.2 /gm) graphite and cokes exhibit excellent reversible lithium intercalation characteristics, making them ideal for use as anodes in high voltage lithium insertion (lithium-ion) batteries. Electrodes having a higher surface area, fabricated from powdered carbon blacks, such as carbon aerogel powder, carbon aerogel microspheres, activated carbons, etc. yield high conductivity carbon compositives with excellent double layer capacity, and can be used in double layer capacitors, or for capacitive deionization and/or waste treatment of liquid streams. By adding metallic catalysts to be high surface area carbons, fuel cell electrodes can be produced.

Fabricating solid carbon porous electrodes from powders

DOEpatents

Kaschmitter, J.L.; Tran, T.D.; Feikert, J.H.; Mayer, S.T.

1997-06-10

Fabrication is described for conductive solid porous carbon electrodes for use in batteries, double layer capacitors, fuel cells, capacitive deionization, and waste treatment. Electrodes fabricated from low surface area (<50 m{sup 2}/gm) graphite and cokes exhibit excellent reversible lithium intercalation characteristics, making them ideal for use as anodes in high voltage lithium insertion (lithium-ion) batteries. Electrodes having a higher surface area, fabricated from powdered carbon blacks, such as carbon aerogel powder, carbon aerogel microspheres, activated carbons, etc. yield high conductivity carbon composites with excellent double layer capacity, and can be used in double layer capacitors, or for capacitive deionization and/or waste treatment of liquid streams. By adding metallic catalysts to high surface area carbons, fuel cell electrodes can be produced. 1 fig.

Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane

NASA Astrophysics Data System (ADS)

He, Ruixuan; Echeverri, Mauricio; Kyu, Thein

2014-03-01

With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.

Megawatt Class Nuclear Space Power Systems (MCNSPS) conceptual design and evaluation report. Volume 1: Objectives, summary results and introduction

NASA Technical Reports Server (NTRS)

Wetch, J. R.

1988-01-01

The objective was to determine which reactor, conversion, and radiator technologies would best fulfill future Megawatt Class Nuclear Space Power System Requirements. Specifically, the requirement was 10 megawatts for 5 years of full power operation and 10 years systems life on orbit. A variety of liquid metal and gas cooled reactors, static and dynamic conversion systems, and passive and dynamic radiators were considered. Four concepts were selected for more detailed study. The concepts are: a gas cooled reactor with closed cycle Brayton turbine-alternator conversion with heat pipe and pumped tube-fin heat rejection; a lithium cooled reactor with a free piston Stirling engine-linear alternator and a pumped tube-fin radiator; a lithium cooled reactor with potassium Rankine turbine-alternator and heat pipe radiator; and a lithium cooled incore thermionic static conversion reactor with a heat pipe radiator. The systems recommended for further development to meet a 10 megawatt long life requirement are the lithium cooled reactor with the K-Rankine conversion and heat pipe radiator, and the lithium cooled incore thermionic reactor with heat pipe radiator.

Separative analyses of a chromatographic column packed with a core-shell adsorbent for lithium isotope separation

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

Sugiyama, T.; Sugura, K.; Enokida, Y.

2015-03-15

Lithium-6 is used as a blanket material for sufficient tritium production in DT fueled fusion reactors. A core-shell type adsorbent was proposed for lithium isotope separation by chromatography. The mass transfer model in a chromatographic column consisted of 4 steps, such as convection and dispersion in the column, transfer through liquid films, intra-particle diffusion and and adsorption or desorption at the local adsorption sites. A model was developed and concentration profiles and time variation in the column were numerically simulated. It became clear that core-shell type adsorbents with thin porous shell were saturated rapidly relatively to fully porous one andmore » established a sharp edge of adsorption band. This is very important feature because lithium isotope separation requires long-distance development of adsorption band. The values of HETP (Height Equivalent of a Theoretical Plate) for core-shell adsorbent packed column were estimated by statistical moments of the step response curve. The value of HETP decreased with the thickness of the porous shell. A core-shell type adsorbent is, then, useful for lithium isotope separation. (authors)« less

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

NASA Astrophysics Data System (ADS)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Design principles for electrolytes and interfaces for stable lithium-metal batteries

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

Tikekar, Mukul D.; Choudhury, Snehashis; Tu, Zhengyuan

2016-09-08

The future of electrochemical energy storage hinges on the advancement of science and technology that enables rechargeable batteries that utilize reactive metals as anodes. With specific capacity more than ten times that of the LiC6 anode used in present-day lithium-ion batteries, cells based on Li-metal anodes are of particular interest. Effective strategies for stabilizing the anode in such cells are now understood to be a requirement for progress on exceptional storage technologies, including Li–S and Li–O2 batteries. Multiple challenges—parasitic reactions of Li-metal with liquid electrolytes, unstable and dendritic electrodeposition, and dendrite-induced short circuits—derailed early efforts to commercialize such lithium-metal batteries.more » Here we consider approaches for rationally designing electrolytes and Li-metal/electrolyte interfaces for stable, dendrite-free operation of lithium-metal batteries. On the basis of fundamental understanding of the failure modes of reactive metal anodes, we discuss the key variables that govern the stability of electrodeposition at the Li anode and propose a universal framework for designing stable electrolytes and interfaces for lithium-metal batteries.« less

Design principles for electrolytes and interfaces for stable lithium-metal batteries

NASA Astrophysics Data System (ADS)

Tikekar, Mukul D.; Choudhury, Snehashis; Tu, Zhengyuan; Archer, Lynden A.

2016-09-01

The future of electrochemical energy storage hinges on the advancement of science and technology that enables rechargeable batteries that utilize reactive metals as anodes. With specific capacity more than ten times that of the LiC6 anode used in present-day lithium-ion batteries, cells based on Li-metal anodes are of particular interest. Effective strategies for stabilizing the anode in such cells are now understood to be a requirement for progress on exceptional storage technologies, including Li-S and Li-O2 batteries. Multiple challenges—parasitic reactions of Li-metal with liquid electrolytes, unstable and dendritic electrodeposition, and dendrite-induced short circuits—derailed early efforts to commercialize such lithium-metal batteries. Here we consider approaches for rationally designing electrolytes and Li-metal/electrolyte interfaces for stable, dendrite-free operation of lithium-metal batteries. On the basis of fundamental understanding of the failure modes of reactive metal anodes, we discuss the key variables that govern the stability of electrodeposition at the Li anode and propose a universal framework for designing stable electrolytes and interfaces for lithium-metal batteries.

Mixed ionic liquid as electrolyte for lithium batteries

NASA Astrophysics Data System (ADS)

Diaw, M.; Chagnes, A.; Carré, B.; Willmann, P.; Lemordant, D.

Ionic liquids like 1-butyl-3-methylimidazolium tetrafluoroborate (IMIBF 4) or hexafluorophosphate (IMIPF 6) and 1-butyl-4-methylpyridinium tetrafluoroborate (PyBF 4) were mixed with organic solvents such as butyrolactone (BL) and acetonitrile (ACN). A lithium salt (LiBF 4 or LiPF 6) was added to these mixtures for possible application in the field of energy storage (batteries or supercapacitors). Viscosities, conductivities and electrochemical windows at a Pt electrode of these electrolytes were investigated. All studied electrolytes are stable toward oxidation and exhibit a vitreous phase transition, which has been determined by application of the VTF theory to conductivity measurements. Mixtures containing the BF 4- anion exhibit the lowest viscosity and the highest conductivity. Two mixtures have been optimized in terms of conductivity: BL/IMIBF 4 (60/40, v/v) and ACN/IMIBF 4 (70/30, v/v).

Investigation of a lithium-halogen exchange flow process for the preparation of boronates by using a cryo-flow reactor.

PubMed

Newby, James A; Huck, Lena; Blaylock, D Wayne; Witt, Paul M; Ley, Steven V; Browne, Duncan L

2014-01-03

Conducting low-temperature organometallic reactions under continuous flow conditions offers the potential to more accurately control exotherms and thus provide more reproducible and scalable processes. Herein, progress towards this goal with regards to the lithium-halogen exchange/borylation reaction is reported. In addition to improving the scope of substrates available on a research scale, methods to improve reaction profiles and expedite purification of the products are also described. On moving to a continuous system, thermocouple measurements have been used to track exotherms and provide a level of safety for continuous processing of organometallic reagents. The use of an in-line continuous liquid-liquid separation device to circumvent labour intensive downstream off-line processing is also reported. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Class of Organopolysulfides As Liquid Cathode Materials for High-Energy-Density Lithium Batteries.

PubMed

Bhargav, Amruth; Bell, Michaela Elaine; Karty, Jonathan; Cui, Yi; Fu, Yongzhu

2018-06-27

Sulfur-based cathodes are promising to enable high-energy-density lithium-sulfur batteries; however, elemental sulfur as active material faces several challenges, including undesirable volume change (∼80%) when completely reduced and high dependence on liquid electrolyte wherein an electrolyte/sulfur ratio >10 μL mg -1 is required for high material utilization. These limit the attainable energy densities of these batteries. Herein, we introduce a new class of phenyl polysulfides C 6 H 5 S x C 6 H 5 (4 ≤ x ≤ 6) as liquid cathode materials synthesized in a facile and scalable route to mitigate these setbacks. These polysulfides possess sufficiently high theoretical specific capacities, specific energies, and energy densities. Spectroscopic techniques verify their chemical composition and computation shows that the volume change when reduced is about 37%. Lithium half-cell testing shows that phenyl hexasulfide (C 6 H 5 S 6 C 6 H 5 ) can provide a specific capacity of 650 mAh g -1 and capacity retention of 80% through 500 cycles at 1 C rate along with superlative performance up to 10 C. Furthermore, 1302 Wh kg -1 and 1720 Wh L -1 are achievable at a low electrolyte/active material ratio, i.e., 3 μL mg -1 . This work adds new members to the cathode family for Li-S batteries, reduces the gap between the theoretical and practical energy densities of batteries, and provides a new direction for the development of alternative high-capacity cathode materials.

MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

PubMed

Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

2013-03-21

Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results.

Electrochemical properties of new organic radical materials for lithium secondary batteries

NASA Astrophysics Data System (ADS)

Lee, Seo Hwan; Kim, Jae-Kwang; Cheruvally, Gouri; Choi, Jae-Won; Ahn, Jou-Hyeon; Chauhan, Ghanshyam S.; Song, Choong Eui

The use of ionic liquid (IL)-supported organic radicals as cathode-active materials in lithium secondary batteries is reported in this article. Two different types of IL-supported organic radicals based on the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical and imidazolium hexafluorophosphate IL were synthesized. The first type is a mono-radical with one unit of TEMPO and the second is a symmetrical di-radical with 2 U of TEMPO; both are viscous liquids at 25 °C. The radicals exhibit electrochemical activity at ∼3.5 V versus Li/Li + as revealed in the cyclic voltammetry tests. The organic radical batteries (ORBs) with these materials as the cathode, a lithium metal anode and 1 M LiPF 6 in EC/DMC electrolyte exhibited good performance at room temperature during the charge-discharge and cycling tests. The batteries exhibited specific capacities of 59 and 80 mAh g -1 at 1 C-rate with the mono- and di-radicals as the cathodes, respectively, resulting in 100% utilization of the materials. The performance degradation with increasing C-rate is very minimal for the ORBs, thus demonstrating good rate capability.

Functional Hybrid Materials Based on Manganese Dioxide and Lignin Activated by Ionic Liquids and Their Application in the Production of Lithium Ion Batteries

PubMed Central

Klapiszewski, Łukasz; Szalaty, Tadeusz J.; Kurc, Beata; Stanisz, Małgorzata; Skrzypczak, Andrzej; Jesionowski, Teofil

2017-01-01

Kraft lignin (KL) was activated using selected ionic liquids (ILs). The activated form of the biopolymer, due to the presence of carbonyl groups, can be used in electrochemical tests. To increase the application potential of the system in electrochemistry, activated lignin forms were combined with manganese dioxide, and the most important physicochemical and morphological-microstructural properties of the novel, functional hybrid systems were determined using Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA), scanning electron microscopy (SEM), zeta potential analysis, thermal stability (TGA/DTG) and porous structure analysis. An investigation was also made of the practical application of the hybrid materials in the production of lithium ion batteries. The capacity of the anode (MnO2/activated lignin), working at a low current regime of 50 mA·g−1, was ca. 610 mAh·g−1, while a current of 1000 mA·g−1 resulted in a capacity of 570 mAh·g−1. Superior cyclic stability and rate capability indicate that this may be a promising electrode material for use in high-performance lithium ion batteries. PMID:28704933

Understanding batteries on the micro- and nanometer scale

ScienceCinema

None

2018-01-16

In order to understand performance limitations and failure mechanisms of batteries, one has to investigate processes on the micro- and nanometer scale. A typical failure mechanism in lithium metal batteries is dendritic growth. During discharge, lithium is stripped of the anode surface and migrates to the cathode. During charge, lithium is deposited back on the anode. Repeated cycling can result in stripping and re-deposition that roughens the surface. The roughening of the surface changes the electric field and draws more metal to spikes that are beginning to grow. These can grow with tremendous mechanical force, puncture the separator, and directly connect the anode with the cathode which can create an internal short circuit. This can lead to an uncontrolled discharge reaction, which heats the cell and causes additional exothermic reactions leading to what is called thermal runaway. ORNL has developed a new technology called liquid electron microscopy. In a specially designed sample holder micro-chamber with electron-transparent windows, researchers can hold a liquid and take images of structures and particles at nanometer size. It's the first microscope holder of its kind used to investigate the inside of a battery while cycled.

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.

Interfaces and Materials in Lithium Ion Batteries: Challenges for Theoretical Electrochemistry.

PubMed

Kasnatscheew, Johannes; Wagner, Ralf; Winter, Martin; Cekic-Laskovic, Isidora

2018-04-18

Energy storage is considered a key technology for successful realization of renewable energies and electrification of the powertrain. This review discusses the lithium ion battery as the leading electrochemical storage technology, focusing on its main components, namely electrode(s) as active and electrolyte as inactive materials. State-of-the-art (SOTA) cathode and anode materials are reviewed, emphasizing viable approaches towards advancement of the overall performance and reliability of lithium ion batteries; however, existing challenges are not neglected. Liquid aprotic electrolytes for lithium ion batteries comprise a lithium ion conducting salt, a mixture of solvents and various additives. Due to its complexity and its role in a given cell chemistry, electrolyte, besides the cathode materials, is identified as most susceptible, as well as the most promising, component for further improvement of lithium ion batteries. The working principle of the most important commercial electrolyte additives is also discussed. With regard to new applications and new cell chemistries, e.g., operation at high temperature and high voltage, further improvements of both active and inactive materials are inevitable. In this regard, theoretical support by means of modeling, calculation and simulation approaches can be very helpful to ex ante pre-select and identify the aforementioned components suitable for a given cell chemistry as well as to understand degradation phenomena at the electrolyte/electrode interface. This overview highlights the advantages and limitations of SOTA lithium battery systems, aiming to encourage researchers to carry forward and strengthen the research towards advanced lithium ion batteries, tailored for specific applications.

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

Lithium Carbonate Recovery from Cathode Scrap of Spent Lithium-Ion Battery: A Closed-Loop Process.

PubMed

Gao, Wenfang; Zhang, Xihua; Zheng, Xiaohong; Lin, Xiao; Cao, Hongbin; Zhang, Yi; Sun, Zhi

2017-02-07

A closed-loop process to recover lithium carbonate from cathode scrap of lithium-ion battery (LIB) is developed. Lithium could be selectively leached into solution using formic acid while aluminum remained as the metallic form, and most of the other metals from the cathode scrap could be precipitated out. This phenomenon clearly demonstrates that formic acid can be used for lithium recovery from cathode scrap, as both leaching and separation reagent. By investigating the effects of different parameters including temperature, formic acid concentration, H 2 O 2 amount, and solid to liquid ratio, the leaching rate of Li can reach 99.93% with minor Al loss into the solution. Subsequently, the leaching kinetics was evaluated and the controlling step as well as the apparent activation energy could be determined. After further separation of the remaining Ni, Co, and Mn from the leachate, Li 2 CO 3 with the purity of 99.90% could be obtained. The final solution after lithium carbonate extraction can be further processed for sodium formate preparation, and Ni, Co, and Mn precipitates are ready for precursor preparation for cathode materials. As a result, the global recovery rates of Al, Li, Ni, Co, and Mn in this process were found to be 95.46%, 98.22%, 99.96%, 99.96%, and 99.95% respectively, achieving effective resources recycling from cathode scrap of spent LIB.

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

Ono, M.; Jaworski, M. A.; Kaita, R.

Steady-state fusion reactor operation presents major divertor technology challenges, including high divertor heat flux both steady-state and transients. In addition to those issues, there are unresolved issues of long term dust accumulation and associated tritium inventory and safety issues. It has been suggested that radiative liquid lithium divertor concepts with a modest lithium-loop could provide a possible solution for these outstanding fusion reactor technology issues while potentially improving the reactor plasma performance. The application of lithium (Li) in NSTX resulted in improved H-mode confinement, H-mode power threshold reduction, and reduction in the divertor peak heat flux while maintaining essentially Li-freemore » core plasma operation even during H-modes. These promising results in NSTX and related modeling calculations motivated the radiative liquid lithium divertor (RLLD) concept and its variant, the active liquid lithium divertor concept (ARLLD), taking advantage of the enhanced Li radiation in relatively poorly confined divertor plasmas. It was estimated that only a few moles/sec of lithium injection would be needed to significantly reduce the divertor heat flux in a tokamak fusion power plant. By operating at lower temperatures ≤ 500°C than the first wall ~ 600 – 700°C, the LL-covered divertor chamber wall surfaces can serve as an effective particle pump, as impurities generally migrate toward lower temperature LL divertor surfaces. To maintain the LL purity, a closed LL loop system with a modest circulating capacity of ~ 1 liter/second (l/sec) is envisioned to sustain the steady-state operation of a 1 GW-electric class fusion power plant. By running the Li loop continuously, it can carry the dust particles and impurities generated in the vacuum vessel to outside where the dust / impurities are removed by relatively simple filter and cold/hot trap systems. Using a cold trap system, it can recover in tritium (T) in real time from LL at a rate of ~ 0.5 g / sec needed to sustain the fusion reaction while minimizing the T inventory issue. With an expected T fraction of ≤ 0.7 %, an acceptable level of T inventory can be achieved. In NSTX-U, preparations are now underway to elucidate the physics of Li plasma interactions with a number of Li application tools and Li radiation spectroscopic instruments. The NSTX-U Li evaporator which provides Li coating over the lower divertor plate, can offer important information on the RLLD concept, and the Li granule injector will test some of the key physics issue on the ARLLD concept. A LL-loop is also being prepared off line for prototyping future use on NSTX-U.« less

The Experimental Study of Rayleigh-Taylor Instability using a Linear Induction Motor Accelerator

NASA Astrophysics Data System (ADS)

Yamashita, Nicholas; Jacobs, Jeffrey

2009-11-01

The experiments to be presented utilize an incompressible system of two stratified miscible liquids of different densities that are accelerated in order to produce the Rayleigh-Taylor instability. Three liquid combinations are used: isopropyl alcohol with water, a calcium nitrate solution or a lithium polytungstate solution, giving Atwood numbers of 0.11, 0.22 and 0.57, respectively. The acceleration required to drive the instability is produced by two high-speed linear induction motors mounted to an 8 m tall drop tower. The motors are mounted in parallel and have an effective acceleration length of 1.7 m and are each capable of producing 15 kN of thrust. The liquid system is contained within a square acrylic tank with inside dimensions 76 x76x184 mm. The tank is mounted to an aluminum plate, which is driven by the motors to create constant accelerations in the range of 1-20 g's, though the potential exists for higher accelerations. Also attached to the plate are a high-speed camera and an LED backlight to provide continuous video of the instability. In addition, an accelerometer is used to provide acceleration measurements during each experiment. Experimental image sequences will be presented which show the development of a random three-dimensional instability from an unforced initial perturbation. Measurements of the mixing zone width will be compared with traditional growth models.

Single lithium-ion conducting solid polymer electrolytes: advances and perspectives.

PubMed

Zhang, Heng; Li, Chunmei; Piszcz, Michal; Coya, Estibaliz; Rojo, Teofilo; Rodriguez-Martinez, Lide M; Armand, Michel; Zhou, Zhibin

2017-02-06

Electrochemical energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aqueous liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues, and the energy density of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theoretical capacity of lithium metal and its low negative potential. However, the progress in the field of non-aqueous liquid electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect solution to these safety concerns and to the enhancement of energy density. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concentration polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorganic backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference number (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on organic polymers, organic-inorganic hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental physical and electrochemical properties of SLIC-SPEs prepared by different methods are discussed in detail. In particular, special attention is paid to the SLIC-SPEs with high ionic conductivity and high LTN. Finally, perspectives on the main challenges and focus on the future research are also presented.

Effect of lithium in the DIII-D SOL and plasma-facing surfaces

NASA Astrophysics Data System (ADS)

Jackson, G. L.; Chrobak, C. P.; McLean, A. G.; Maingi, R.; Mansfield, D. K.; Roquemore, A. L.; Diwakar, P.; Hassanein, A.; Lietz, A.; Rudakov, D. L.; Sizyuk, T.; Tripathi, J.

2015-08-01

Lithium has been introduced into the DIII-D tokamak, and migration and retention in graphite have been characterized since no lithium was present in DIII-D initially. A new regime with an enhanced edge electron pedestal and H98y2 ⩽ 2 has been obtained with lithium. Lithium deposition was not uniform, but rather preferentially deposited near the strike points, consistent with previous 13C experiments. Edge visible lithium light (LiI) remained well above the previous background during the entire DIII-D campaign, decaying with a 2600 plasma-second e-fold, but plasma performance was only affected on the discharge with lithium injection. Lithium injection demonstrated the capability of reducing hydrogenic recycling, density, and ELM frequency. Graphite and silicon samples were exposed to a lithium-injected discharge, using the DiMES system and then removed for ex-situ analysis. The deposited lithium layer remained detectable to a depth up to 1 μm.

Enantioselective Effect of Flurbiprofen on Lithium Disposition in Rats.

PubMed

Uwai, Yuichi; Matsumoto, Masashi; Kawasaki, Tatsuya; Nabekura, Tomohiro

2017-01-01

Lithium is administered for treating bipolar disorders and is mainly excreted into urine. Nonsteroidal anti-inflammatory drugs inhibit this process. In this study, we examined the enantioselective effect of flurbiprofen on the disposition of lithium in rats. Pharmacokinetic experiments with lithium were performed. Until 60 min after the intravenous administration of lithium chloride at 30 mg/kg as a bolus, 17.8% of lithium injected was recovered into the urine. Its renal clearance was calculated to be 1.62 mL/min/kg. Neither creatinine clearance (Ccr) nor pharmacokinetics of lithium was affected by the simultaneous injection of (R)-flurbiprofen at 20 mg/kg. (S)-flurbiprofen impaired the renal function and interfered with the urinary excretion of lithium. The ratio of renal clearance of lithium to Ccr was decreased by the (S)-enantiomer. This study clarified that the (S)-flurbiprofen but not (R)-flurbiprofen inhibited the renal excretion of lithium in rats. © 2017 S. Karger AG, Basel.

Upgraded flowing liquid lithium limiter for improving Li coverage uniformity and erosion resistance in EAST device

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

Zuo, G. Z.; Hu, J. S.; Maingi, R.

In this paper, we report on design and technology improvements for a flowing liquid lithium (FLiLi) limiter inserted into auxiliary heated discharges in the experimental advanced superconducting tokamak device. In order to enhance Li coverage uniformity and erosion resistance, a new liquid Li distributor with homogenous channels was implemented. In addition, two independent electromagnetic pumps and a new horizontal capillary structure contributed to an improvement in the observed Li flow uniformity (from 30% in the previous FLiLi design to >80% in this FLiLi design). To improve limiter surface erosion resistance, hot isostatic press technology was applied, which improved the thermalmore » contact between thin stainless steel protective layers covering the Cu heat sink. The thickness of the stainless steel layer was increased from 0.1 mm to 0.5 mm, which also helped macroscopic erosion resilience. Finally, despite the high auxiliary heating power up to 4.5 MW, no Li bursts were recorded from FLiLi, underscoring the improved performance of this new design.« less

Upgraded flowing liquid lithium limiter for improving Li coverage uniformity and erosion resistance in EAST device

DOE PAGES

Zuo, G. Z.; Hu, J. S.; Maingi, R.; ...

2017-12-14

In this paper, we report on design and technology improvements for a flowing liquid lithium (FLiLi) limiter inserted into auxiliary heated discharges in the experimental advanced superconducting tokamak device. In order to enhance Li coverage uniformity and erosion resistance, a new liquid Li distributor with homogenous channels was implemented. In addition, two independent electromagnetic pumps and a new horizontal capillary structure contributed to an improvement in the observed Li flow uniformity (from 30% in the previous FLiLi design to >80% in this FLiLi design). To improve limiter surface erosion resistance, hot isostatic press technology was applied, which improved the thermalmore » contact between thin stainless steel protective layers covering the Cu heat sink. The thickness of the stainless steel layer was increased from 0.1 mm to 0.5 mm, which also helped macroscopic erosion resilience. Finally, despite the high auxiliary heating power up to 4.5 MW, no Li bursts were recorded from FLiLi, underscoring the improved performance of this new design.« less

Effects of Ultrasonic Vibration on Heat Transfer Characteristics of Lithium Bromide Aqueous Solution under the Reduced Pressure

NASA Astrophysics Data System (ADS)

Yamashiro, Hikaru; Nakashima, Ryou

The effects of ultrasonic vibration on heat transfer characteristics of lithium bromide aqueous solution under the reduced pressures are studied experimentally. Pool boiling curves on horizontal smooth tube are obtained using distilled water and 50 % LiBr aqueous solution as test liquids. The system pressure p is varied from 12 to 101 kPa and the liquid subcooling ΔTsub ranges from 0 to 70 K. The frequency of ultrasonic vibration vi s set at 24 and 44 kHz, and the power input to the vibrator P is varied from 0 to 35 W. The wall superheat at the boiling incipience is found to decrease with increasing P, and the nucleate boiling curve shifts toward the lower wall temperature region. However, the effect of P is not found to be very significant in the high heat flux region, especially in the case of small liquid subcooling. Ultrasonic vibration is also found to improve the nucleate boiling heat transfer coefficient by up to a maximum of 3.5 times and to prevent crystallization of the solution and precipitation of additives.

Novel thermal management system using boiling cooling for high-powered lithium-ion battery packs for hybrid electric vehicles

NASA Astrophysics Data System (ADS)

Al-Zareer, Maan; Dincer, Ibrahim; Rosen, Marc A.

2017-09-01

A thermal management system is necessary to control the operating temperature of the lithium ion batteries in battery packs for electrical and hybrid electrical vehicles. This paper proposes a new battery thermal management system based on one type of phase change material for the battery packs in hybrid electrical vehicles and develops a three dimensional electrochemical thermal model. The temperature distributions of the batteries are investigated under various operating conditions for comparative evaluations. The proposed system boils liquid propane to remove the heat generated by the batteries, and the propane vapor is used to cool the part of the battery that is not covered with liquid propane. The effect on the thermal behavior of the battery pack of the height of the liquid propane inside the battery pack, relative to the height of the battery, is analyzed. The results show that the propane based thermal management system provides good cooling control of the temperature of the batteries under high and continuous charge and discharge cycles at 7.5C.

Characterization of the liquid Li-solid Mo (1 1 0) interface from classical molecular dynamics for plasma-facing applications

DOE PAGES

Vella, Joseph R.; Chen, Mohan; Fürstenberg, Sven; ...

2017-08-11

An understanding of the wetting properties and a characterization of theinterface between liquid lithium (Li) and solid molybdenum (Mo) are relevant to assessing the efficacy of Li as a plasma-facing component in fusion reactors. Here, a new second-nearest neighbor modified embedded-atom method (2NN MEAM) force eld is parameterized to describe the interactions between Li and Mo. The new force eld reproduces several benchmark properties obtained from first-principles quantum mechanics simulations, including binding curves for Li at three different adsorption sites and the corresponding forces on Li atoms adsorbed on the Mo (110) surface. This force field is then used tomore » study the wetting of liquid Li on the (110) surface of Mo and to examine the Li-Mo interface using molecular dynamics simulations. From droplet simulations, we nd that liquid Li tends to completely wet the perfect Mo (110) surface, in contradiction with previous experimental measurements that found non-zero contact angles for liquid Li on a Mo substrate. However, these experiments were not carried out under ultra-high vacuum conditions or with a perfect (110) Mo surface, suggesting that the presence of impurities, such as oxygen, and surface structure play a crucial role in this wetting process. From thin- lm simulations, it is observed that the first layer of Li on the Mo (110) surface has many solid-like properties such as a low mobility and a larger degree of ordering when compared to layers further away from the surface, even at temperatures well above the bulk melting temperature of Li. Our findings are consistent with temperature-programmed desorption experiments.« less

Characterization of the liquid Li-solid Mo (1 1 0) interface from classical molecular dynamics for plasma-facing applications

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

Vella, Joseph R.; Chen, Mohan; Fürstenberg, Sven

An understanding of the wetting properties and a characterization of theinterface between liquid lithium (Li) and solid molybdenum (Mo) are relevant to assessing the efficacy of Li as a plasma-facing component in fusion reactors. Here, a new second-nearest neighbor modified embedded-atom method (2NN MEAM) force eld is parameterized to describe the interactions between Li and Mo. The new force eld reproduces several benchmark properties obtained from first-principles quantum mechanics simulations, including binding curves for Li at three different adsorption sites and the corresponding forces on Li atoms adsorbed on the Mo (110) surface. This force field is then used tomore » study the wetting of liquid Li on the (110) surface of Mo and to examine the Li-Mo interface using molecular dynamics simulations. From droplet simulations, we nd that liquid Li tends to completely wet the perfect Mo (110) surface, in contradiction with previous experimental measurements that found non-zero contact angles for liquid Li on a Mo substrate. However, these experiments were not carried out under ultra-high vacuum conditions or with a perfect (110) Mo surface, suggesting that the presence of impurities, such as oxygen, and surface structure play a crucial role in this wetting process. From thin- lm simulations, it is observed that the first layer of Li on the Mo (110) surface has many solid-like properties such as a low mobility and a larger degree of ordering when compared to layers further away from the surface, even at temperatures well above the bulk melting temperature of Li. Our findings are consistent with temperature-programmed desorption experiments.« less

Characterization of the liquid Li-solid Mo (1 1 0) interface from classical molecular dynamics for plasma-facing applications

NASA Astrophysics Data System (ADS)

Vella, Joseph R.; Chen, Mohan; Fürstenberg, Sven; Stillinger, Frank H.; Carter, Emily A.; Debenedetti, Pablo G.; Panagiotopoulos, Athanassios Z.

2017-11-01

An understanding of the wetting properties and a characterization of the interface between liquid lithium (Li) and solid molybdenum (Mo) are relevant to assessing the efficacy of Li as a plasma-facing component in fusion reactors. In this work, a new second-nearest neighbor modified embedded-atom method (2NN MEAM) force field is parameterized to describe the interactions between Li and Mo. The new force field reproduces several benchmark properties obtained from first-principles quantum mechanics simulations, including binding curves for Li at three different adsorption sites and the corresponding forces on Li atoms adsorbed on the Mo (1 1 0) surface. This force field is then used to study the wetting of liquid Li on the (1 1 0) surface of Mo and to examine the Li-Mo interface using molecular dynamics simulations. From droplet simulations, we find that liquid Li tends to completely wet the perfect Mo (1 1 0) surface, in contradiction with previous experimental measurements that found non-zero contact angles for liquid Li on a Mo substrate. However, these experiments were not carried out under ultra-high vacuum conditions or with a perfect (1 1 0) Mo surface, suggesting that the presence of impurities, such as oxygen, and surface structure play a crucial role in this wetting process. From thin-film simulations, it is observed that the first layer of Li on the Mo (1 1 0) surface has many solid-like properties such as a low mobility and a larger degree of ordering when compared to layers further away from the surface, even at temperatures well above the bulk melting temperature of Li. These findings are consistent with temperature-programmed desorption experiments.

Synthesis and Electrochemical Properties of Amorphous Carbon Coated Sn Anode Material for Lithium Ion Batteries and Sodium Ion Batteries.

PubMed

Choi, Ji-Seub; Lee, Hoi-Jin; Ha, Jong-Keun; Cho, Kwon-Koo

2018-09-01

Sn is one of the promising anode material for lithium-ion and sodium-ion batteries because of Sn has many advantages such as a high theoretical capacity of 994 mAh/g, inexpensive, abundant and nontoxic. However, Sn-based anodes have a critical problem from pulverization of the particles due to large volume change (>300% in lithium-ion battery and 420% in the sodium-ion battery) during alloying/dealloying reaction. To overcome this problem, we fabricate Sn/C particle of core/shell structure. Sn powder was produced by pulsed wire explosion in liquid media, and amorphous carbon coating process was prepared by hydrothermal synthesis. The charge capacity of Sn electrode and amorphous carbon coated Sn electrode was 413 mAh/g and 452 mAh/g after 40 cycles in lithium half-cell test. The charge capacity of Sn electrode and amorphous carbon coated Sn electrode was 240 mAh/g and 487 mAh/g after 40 cycles in sodium half-cell test. Amorphous carbon coating contributed to the improvement of capacity in lithium and sodium battery systems. And the effect of amorphous carbon coating in sodium battery system was superior to that in lithium battery system.

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.

Ab Initio Simulations and Electronic Structure of Lithium-Doped Ionic Liquids: Structure, Transport, and Electrochemical Stability.

PubMed

Haskins, Justin B; Bauschlicher, Charles W; Lawson, John W

2015-11-19

Density functional theory (DFT), density functional theory molecular dynamics (DFT-MD), and classical molecular dynamics using polarizable force fields (PFF-MD) are employed to evaluate the influence of Li(+) on the structure, transport, and electrochemical stability of three potential ionic liquid electrolytes: N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([pyr14][TFSI]), N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]). We characterize the Li(+) solvation shell through DFT computations of [Li(Anion)n]((n-1)-) clusters, DFT-MD simulations of isolated Li(+) in small ionic liquid systems, and PFF-MD simulations with high Li-doping levels in large ionic liquid systems. At low levels of Li-salt doping, highly stable solvation shells having two to three anions are seen in both [pyr14][TFSI] and [pyr13][FSI], whereas solvation shells with four anions dominate in [EMIM][BF4]. At higher levels of doping, we find the formation of complex Li-network structures that increase the frequency of four anion-coordinated solvation shells. A comparison of computational and experimental Raman spectra for a wide range of [Li(Anion)n]((n-1)-) clusters shows that our proposed structures are consistent with experiment. We then compute the ion diffusion coefficients and find measures from small-cell DFT-MD simulations to be the correct order of magnitude, but influenced by small system size and short simulation length. Correcting for these errors with complementary PFF-MD simulations, we find DFT-MD measures to be in close agreement with experiment. Finally, we compute electrochemical windows from DFT computations on isolated ions, interacting cation/anion pairs, and liquid-phase systems with Li-doping. For the molecular-level computations, we generally find the difference between ionization energy and electron affinity from isolated ions and interacting cation/anion pairs to provide upper and lower bounds, respectively, to experiment. In the liquid phase, we find the difference between the lowest unoccupied and highest occupied electronic levels in pure and hybrid functionals to provide lower and upper bounds, respectively, to experiment. Li-doping in the liquid-phase systems results in electrochemical windows little changed from the neat systems.

Preparation of refractory cermet structures for lithium compatibility testing

NASA Technical Reports Server (NTRS)

Heestand, R. L.; Jones, R. A.; Wright, T. R.; Kizer, D. E.

1973-01-01

High-purity nitride and carbide cermets were synthesized for compatability testing in liquid lithium. A process was developed for the preparation of high-purity hafnium nitride powder, which was subsequently blended with tungsten powder or tantalum nitride and tungsten powders and fabricated into 3 in diameter billets by uniaxial hot pressing. Specimens were then cut from the billets for compatability testing. Similar processing techniques were applied to produce hafnium carbide and zirconium carbide cermets for use in the testing program. All billets produced were characterized with respect to chemistry, structure, density, and strength properties.

Helium Nanodroplet Isolation and Infrared Spectroscopy of the Isolated Ion-Pair 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

DTIC Science & Technology

2013-09-01

Use in Lithium Metal-Polymer Electrolyte Batteries. J. Electrochem. Soc. 2005, 152, A978-A983.     4. Henderson, W. A.; Shin, J. H.; Passerini, S...Chen, L. Q.; Hu, Y. S.; Li, H.; Huang, X. J. Novel Room Temperature Molten Salt Electrolyte Based on Litfsi and Acetamide for Lithium Batteries...the Structure of Ionic Liquid 1-Ethyl-3- Methylimidazolium Hexafluorophosphate . Chinese J. Struc. Chem. 2005, 24, 576-580.     37. Liu, K. H.; Pu, M

Structural properties of lead-lithium alloys

NASA Astrophysics Data System (ADS)

Khambholja, S. G.; Satikunvar, D. D.; Abhishek, Agraj; Thakore, B. Y.

2018-05-01

Lead-Lihtium alloys have found large number of applications as liquid metal coolants in nuclear reactors. Large number of experimental work is reported for this system. However, complete theoretical description is still rare. In this scenario, we in the present work report the study of ground state properties of Lead-Lithium system. The present study is performed using plane wave pseudopotential density functional theory as implemented in Quantum ESPRESSO package. The theoretical findings are in agreement with previously reported experimental data. Some conclusions are drawn based on present study, which will be helpful for a comprehensive study.

Maglev Facility for Simulating Variable Gravity

NASA Technical Reports Server (NTRS)

Liu, Yuanming; Strayer, Donald M.; Israelsson, Ulf E.

2010-01-01

An improved magnetic levitation apparatus ("Maglev Facility") has been built for use in experiments in which there are requirements to impose variable gravity (including zero gravity) in order to assess the effects of gravity or the absence thereof on physical and physiological processes. The apparatus is expected to be especially useful for experiments on the effects of gravity on convection, boiling, and heat transfer in fluids and for experiments on mice to gain understanding of bone loss induced in human astronauts by prolonged exposure to reduced gravity in space flight. The maglev principle employed by the apparatus is well established. Diamagnetic cryogenic fluids such as liquid helium have been magnetically levitated for studying their phase transitions and critical behaviors. Biological entities consist mostly of diamagnetic molecules (e.g., water molecules) and thus can be levitated by use of sufficiently strong magnetic fields having sufficiently strong vertical gradients. The heart of the present maglev apparatus is a vertically oriented superconducting solenoid electromagnet (see figure) that generates a static magnetic field of about 16 T with a vertical gradient sufficient for levitation of water in normal Earth gravity. The electromagnet is enclosed in a Dewar flask having a volume of 100 L that contains liquid helium to maintain superconductivity. The Dewar flask features a 66-mm-diameter warm bore, lying within the bore of the magnet, wherein experiments can be performed at room temperature. The warm bore is accessible from its top and bottom ends. The superconducting electromagnet is run in the persistent mode, in which the supercurrent and the magnetic field can be maintained for weeks with little decay, making this apparatus extremely cost and energy efficient to operate. In addition to water, this apparatus can levitate several common fluids: liquid hydrogen, liquid oxygen, methane, ammonia, sodium, and lithium, all of which are useful, variously, as rocket fuels or as working fluids for heat transfer devices. A drop of water 45 mm in diameter and a small laboratory mouse have been levitated in this apparatus.

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.

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

Physicochemical and electrochemical properties of N-methyl-N-methoxymethylpyrrolidinium bis(fluorosulfonyl)amide and its lithium salt composites

NASA Astrophysics Data System (ADS)

Horiuchi, Shunsuke; Yoshizawa-Fujita, Masahiro; Takeoka, Yuko; Rikukawa, Masahiro

2016-09-01

The ionic liquid (IL) N-Methyl-N-methoxymethylpyrrolidinium bis(fluorosulfonyl)amide ([Pyr1,1O1][FSA]) was synthesized, and its physicochemical and electrochemical properties were investigated with respect to its application as an electrolyte in lithium-ion secondary batteries operating over a wide temperature range. [Pyr1,1O1][FSA]/Li salt (0.34 mol kg-1) composites were prepared by adding lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) into the IL. [Pyr1,1O1][FSA] and [Pyr1,1O1][FSA]/LiTFSA exhibited melting temperatures (Tm) below -30 °C. [Pyr1,1O1][FSA] exhibited a higher ionic conductivity value as compared with that of the corresponding IL with only alkyl substituents. The electrochemical window for both [Pyr1,1O1][FSA] and [Pyr1,1O1][FSA]/LiTFSA was 5.1 V. Stable lithium deposition and dissolution occurred on a Ni electrode at 25 °C.

Synthesis of One-Dimensional and Hyperbranched Nanomaterials for Lithium-Ion Battery Solid Electrolytes

NASA Astrophysics Data System (ADS)

Yang, Ting

Lithium-ion batteries can fail and catch fire when overcharged, exposed to high temperatures or short-circuited due to the highly flammable organic liquid used in the electrolyte. Using inorganic solid electrolyte materials can potentially improve the safety factor. Additionally, nanostructured electrolyte materials may further enhanced performance by taking advantage of their large aspect ratio. In this work, the synthesis of two promising nanostructured solid electrolyte materials was explored. Amorphous lithium niobate nanowires were synthesized through the decomposition of a niobium-containing complex in a structure-directing solvent using a reflux method. Lithium lanthanum titanate was obtained via solid state reaction with titanium oxide nanowires as the titanium precursor, but the nanowire morphology could not be preserved due to high temperature sintering. Hyperbranched potassium lanthanum titanate was synthesized through hydrothermal route. This was the first time that hyperbranched nanowires with perovskite structure were made without any catalyst or substrate. This result has the potential to be applied to other perovskite materials.

All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode.

PubMed

Zhu, Zhiqiang; Hong, Meiling; Guo, Dongsheng; Shi, Jifu; Tao, Zhanliang; Chen, Jun

2014-11-26

The cathode capacity of common lithium ion batteries (LIBs) using inorganic electrodes and liquid electrolytes must be further improved. Alternatively, all-solid-state lithium batteries comprising the electrode of organic compounds can offer much higher capacity. Herein, we successfully fabricated an all-solid-state lithium battery based on organic pillar[5]quinone (C35H20O10) cathode and composite polymer electrolyte (CPE). The poly(methacrylate) (PMA)/poly(ethylene glycol) (PEG)-LiClO4-3 wt % SiO2 CPE has an optimum ionic conductivity of 0.26 mS cm(-1) at room temperature. Furthermore, pillar[5]quinine cathode in all-solid-state battery rendered an average operation voltage of ∼2.6 V and a high initial capacity of 418 mAh g(-1) with a stable cyclability (94.7% capacity retention after 50 cycles at 0.2C rate) through the reversible redox reactions of enolate/quinonid carbonyl groups, showing favorable prospect for the device application with high capacity.

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.

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.

Molecular beam epitaxy growth of niobium oxides by solid/liquid state oxygen source and lithium assisted metal-halide chemistry

NASA Astrophysics Data System (ADS)

Tellekamp, M. Brooks; Greenlee, Jordan D.; Shank, Joshua C.; Doolittle, W. Alan

2015-09-01

In order to consistently grow high quality niobium oxides and lithium niobium oxides, a novel solid/liquid state oxygen source, LiClO4, has been implemented in a molecular beam epitaxy (MBE) system. LiClO4 is shown to decompose into both molecular and atomic oxygen upon heating. This allows oxidation rates similar to that of molecular oxygen but at a reduced overall beam flux, quantified by in situ Auger analysis. LiClO4 operation is decomposition limited to less than 400 °C, and other material limitations are identified. The design of a custom near-ambient NbCl5 effusion cell is presented, which improves both short and long term stability. Films of Nb oxidation state +2, +3, and +5 are grown using these new tools, including the multi-functional sub-oxide LiNbO2.

Development and Characterization of Poly(1-vinylpyrrolidone-co-vinyl acetate) Copolymer Based Polymer Electrolytes

PubMed Central

Sa'adun, Nurul Nadiah; Subramaniam, Ramesh; Kasi, Ramesh

2014-01-01

Gel polymer electrolytes (GPEs) are developed using poly(1-vinylpyrrolidone-co-vinyl acetate) [P(VP-co-VAc)] as the host polymer, lithium bis(trifluoromethane) sulfonimide [LiTFSI] as the lithium salt and ionic liquid, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [EMImTFSI] by using solution casting technique. The effect of ionic liquid on ionic conductivity is studied and the optimum ionic conductivity at room temperature is found to be 2.14 × 10−6 S cm−1 for sample containing 25 wt% of EMImTFSI. The temperature dependence of ionic conductivity from 303 K to 353 K exhibits Arrhenius plot behaviour. The thermal stability of the polymer electrolyte system is studied by using thermogravimetric analysis (TGA) while the structural and morphological properties of the polymer electrolyte is studied by using Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction analysis (XRD), respectively. PMID:25431781

Characteristics of fundamental acoustic wave modes in thin piezoelectric plates.

PubMed

Joshi, S G; Zaitsev, B D; Kuznetsova, I E; Teplykh, A A; Pasachhe, A

2006-12-22

The characteristics of the three lowest order plate waves (A(0), S(0), and SH(0)) propagating in piezoelectric plates whose thickness h is much less than the acoustic wavelength lambda are theoretically analyzed. It is found that these waves can provide much higher values of electromechanical coupling coefficient K(2) and lower values of temperature coefficient of delay (TCD) than is possible with surface acoustic waves (SAWs). For example, in 30Y-X lithium niobate, the SH(0) mode has K(2)=0.46 and TCD=55 ppm/degrees C. The corresponding values for SAW in the widely used, strong coupling material of 128Y-X lithium niobate are K(2)=0.053 and TCD=75 ppm/degrees C. Another important advantage of plate waves is that, unlike the case of SAWs, they can operate satisfactorily in contact with a liquid medium, thus making possible their use in liquid phase sensors.

Electronic and structural transitions in dense liquid sodium.

PubMed

Raty, Jean-Yves; Schwegler, Eric; Bonev, Stanimir A

2007-09-27

At ambient conditions, the light alkali metals are free-electron-like crystals with a highly symmetric structure. However, they were found recently to exhibit unexpected complexity under pressure. It was predicted from theory--and later confirmed by experiment--that lithium and sodium undergo a sequence of symmetry-breaking transitions, driven by a Peierls mechanism, at high pressures. Measurements of the sodium melting curve have subsequently revealed an unprecedented (and still unexplained) pressure-induced drop in melting temperature from 1,000 K at 30 GPa down to room temperature at 120 GPa. Here we report results from ab initio calculations that explain the unusual melting behaviour in dense sodium. We show that molten sodium undergoes a series of pressure-induced structural and electronic transitions, analogous to those observed in solid sodium but commencing at much lower pressure in the presence of liquid disorder. As pressure is increased, liquid sodium initially evolves by assuming a more compact local structure. However, a transition to a lower-coordinated liquid takes place at a pressure of around 65 GPa, accompanied by a threefold drop in electrical conductivity. This transition is driven by the opening of a pseudogap, at the Fermi level, in the electronic density of states--an effect that has not hitherto been observed in a liquid metal. The lower-coordinated liquid emerges at high temperatures and above the stability region of a close-packed free-electron-like metal. We predict that similar exotic behaviour is possible in other materials as well.

Taste-aversion learning produced by combined treatment with subthreshold radiation and lithium chloride

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

Rabin, B.M.; Hunt, W.A.; Lee, J.

1987-01-01

These experiments were designed to determine whether treatment with two subthreshold doses of radiation or lithium chloride, either alone or in combination, could lead to taste-aversion learning. The first experiment determined the threshold for a radiation-induced taste aversion at 15-20 rad and for lithium chloride at 0.30-0.45 mEq/kg. In the second experiment it was shown that exposing rats to two doses of 15 rad separated by up to 3 hr produced a taste aversion. Treatment with two injections of lithium chloride did produce a taste aversion when the two treatments were administered within 1 hr or each other. The resultsmore » are discussed in terms of the implications of these findings for understanding the nature of the unconditional stimuli leading to the acquisition of a conditioned taste aversion.« less

Observation of Flat Electron Temperature Profiles in the Lithium Tokamak Experiment

DOE PAGES

Boyle, D. P.; Majeski, R.; Schmitt, J. C.; ...

2017-07-05

It has been predicted for over a decade that low-recycling plasma-facing components in fusion devices would allow high edge temperatures and flat or nearly flat temperature profiles. In recent experiments with lithium wall coatings in the Lithium Tokamak Experiment (LTX), a hot edge ( > 200 eV ) and flat electron temperature profiles have been measured following the termination of external fueling. In this work, reduced recycling was demonstrated by retention of ~ 60% of the injected hydrogen in the walls following the discharge. Electron energy confinement followed typical Ohmic confinement scaling during fueling, but did not decrease with densitymore » after fueling terminated, ultimately exceeding the scaling by ~ 200% . Lastly, achievement of the low-recycling, hot edge regime has been an important goal of LTX and lithium plasma-facing component research in general, as it has potentially significant implications for the operation, design, and cost of fusion devices.« less

Observation of Flat Electron Temperature Profiles in the Lithium Tokamak Experiment

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

Boyle, D. P.; Majeski, R.; Schmitt, J. C.

It has been predicted for over a decade that low-recycling plasma-facing components in fusion devices would allow high edge temperatures and flat or nearly flat temperature profiles. In recent experiments with lithium wall coatings in the Lithium Tokamak Experiment (LTX), a hot edge ( > 200 eV ) and flat electron temperature profiles have been measured following the termination of external fueling. In this work, reduced recycling was demonstrated by retention of ~ 60% of the injected hydrogen in the walls following the discharge. Electron energy confinement followed typical Ohmic confinement scaling during fueling, but did not decrease with densitymore » after fueling terminated, ultimately exceeding the scaling by ~ 200% . Lastly, achievement of the low-recycling, hot edge regime has been an important goal of LTX and lithium plasma-facing component research in general, as it has potentially significant implications for the operation, design, and cost of fusion devices.« less

In situ recording of particle network formation in liquids by ion conductivity measurements.

PubMed

Pfaffenhuber, Christian; Sörgel, Seniz; Weichert, Katja; Bele, Marjan; Mundinger, Tabea; Göbel, Marcus; Maier, Joachim

2011-09-21

The formation of fractal silica networks from a colloidal initial state was followed in situ by ion conductivity measurements. The underlying effect is a high interfacial lithium ion conductivity arising when silica particles are brought into contact with Li salt-containing liquid electrolytes. The experimental results were modeled using Monte Carlo simulations and tested using confocal fluorescence laser microscopy and ζ-potential measurements.

The effects of reduced dopamine transporter function and chronic lithium on motivation, probabilistic learning, and neurochemistry in mice: Modeling bipolar mania.

PubMed

Milienne-Petiot, Morgane; Kesby, James P; Graves, Mary; van Enkhuizen, Jordy; Semenova, Svetlana; Minassian, Arpi; Markou, Athina; Geyer, Mark A; Young, Jared W

2017-02-01

Bipolar disorder (BD) mania patients exhibit poor cognition and reward-seeking/hypermotivation, negatively impacting a patient's quality of life. Current treatments (e.g., lithium), do not treat such deficits. Treatment development has been limited due to a poor understanding of the neural mechanisms underlying these behaviors. Here, we investigated putative mechanisms underlying cognition and reward-seeking/motivational changes relevant to BD mania patients using two validated mouse models and neurochemical analyses. The effects of reducing dopamine transporter (DAT) functioning via genetic (knockdown vs. wild-type littermates), or pharmacological (GBR12909- vs. vehicle-treated C57BL/6J mice) means were assessed in the probabilistic reversal learning task (PRLT), and progressive ratio breakpoint (PRB) test, during either water or chronic lithium treatment. These tasks quantify reward learning and effortful motivation, respectively. Neurochemistry was performed on brain samples of DAT mutants ± chronic lithium using high performance liquid chromatography. Reduced DAT functioning increased reversals in the PRLT, an effect partially attenuated by chronic lithium. Chronic lithium alone slowed PRLT acquisition. Reduced DAT functioning increased motivation (PRB), an effect attenuated by lithium in GBR12909-treated mice. Neurochemical analyses revealed that DAT knockdown mice exhibited elevated homovanillic acid levels, but that lithium had no effect on these elevated levels. Reducing DAT functioning recreates many aspects of BD mania including hypermotivation and improved reversal learning (switching), as well as elevated homovanillic acid levels. Chronic lithium only exerted main effects, impairing learning and elevating norepinephrine and serotonin levels of mice, not specifically treating the underlying mechanisms identified in these models. Copyright © 2016 Elsevier Ltd. All rights reserved.

Lithium wall conditioning by high frequency pellet injection in RFX-mod

NASA Astrophysics Data System (ADS)

Innocente, P.; Mansfield, D. K.; Roquemore, A. L.; Agostini, M.; Barison, S.; Canton, A.; Carraro, L.; Cavazzana, R.; De Masi, G.; Fassina, A.; Fiameni, S.; Grando, L.; Rais, B.; Rossetto, F.; Scarin, P.

2015-08-01

In the RFX-mod reversed field pinch experiment, lithium wall conditioning has been tested with multiple scopes: to improve density control, to reduce impurities and to increase energy and particle confinement time. Large single lithium pellet injection, lithium capillary-pore system and lithium evaporation has been used for lithiumization. The last two methods, which presently provide the best results in tokamak devices, have limited applicability in the RFX-mod device due to the magnetic field characteristics and geometrical constraints. On the other side, the first mentioned technique did not allow injecting large amount of lithium. To improve the deposition, recently in RFX-mod small lithium multi-pellets injection has been tested. In this paper we compare lithium multi-pellets injection to the other techniques. Multi-pellets gave more uniform Li deposition than evaporator, but provided similar effects on plasma parameters, showing that further optimizations are required.

A Lithium Abundance Study of Solar-type Stars in Blanco 1 using the 2.1m McDonald Telescope: Developing Undergraduate Research Experiences.

NASA Astrophysics Data System (ADS)

Cargile, Phillip; James, D. J.; Villalon, K.; Girgenti, S.; Mermilliod, J.

2007-12-01

We present a new catalog of lithium equivalent widths for 20 solar-type stars in the young (60-100 Myr), nearby (250 pc) open cluster Blanco 1, measured from high-resolution spectra (R 30,000), taken during an observing run on the 2.1m telescope at McDonald Observatory. These new lithium data, coupled with the 20 or so extant measurements in the literature, are used in combination with the results of a recently completed standardized BVIc CCD survey, and corresponding 2MASS near-infrared colors, to derive precise lithium abundances for solar-type stars in Blanco 1. Comparing these new results with the existing lithium dataset for other open clusters, we investigate the mass- and age-dependent lithium depletion distribution among early-epoch (< 1Gyr) solar-type stars, and specifically, the lithium abundance scatter as a function of mass in Blanco 1. Our scientific project is highly synergystic with a pedagogical philosophy. We have instituted a program whereby undergraduate students - typically majoring in Liberal Arts and performing an independent study in Astronomy - receive hands-on research experience observing with the 2.1m telescope at the McDonald Observatory. After their observing run, these undergraduates take part in the reduction and analysis of the acquired spectra, and their research experience typically culminates in writing an undergraduate thesis and/or giving a professional seminar to the Astronomy group at Vanderbilt University.

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

Promotion of Organic Reactions by Ultrasound: Coupling of Alkyl and Aryl Halides in the Presence of Lithium Metal and Ultrasound.

ERIC Educational Resources Information Center

Lash, Timothy D.; Berry, Donna

1985-01-01

Experiments involving the coupling of alkyl and aryl halides in the presence of lithium metal and ultrasound are described. The experiments illustrate classical Wurtz and Fittig reactions in addition to being a convenient application of organic sonochemistry. (JN)

Megawatt Class Nuclear Space Power Systems (MCNSPS) conceptual design and evaluation report. Volume 4: Concepts selection, conceptual designs, recommendations

NASA Technical Reports Server (NTRS)

Wetch, J. R.

1988-01-01

A study was conducted by NASA Lewis Research Center for the Triagency SP-100 program office. The objective was to determine which reactor, conversion and radiator technologies would best fulfill future Megawatt Class Nuclear Space Power System Requirements. The requirement was 10 megawatts for 5 years of full power operation and 10 years system life on orbit. A variety of liquid metal and gas cooled reactors, static and dynamic conversion systems, and passive and dynamic radiators were considered. Four concepts were selected for more detailed study: (1) a gas cooled reactor with closed cycle Brayton turbine-alternator conversion with heatpipe and pumped tube fin rejection, (2) a Lithium cooled reactor with a free piston Stirling engine-linear alternator and a pumped tube-fin radiator,(3) a Lithium cooled reactor with a Potassium Rankine turbine-alternator and heat pipe radiator, and (4) a Lithium cooled incore thermionic static conversion reactor with a heat pipe radiator. The systems recommended for further development to meet a 10 megawatt long life requirement are the Lithium cooled reactor with the K-Rankine conversion and heat pipe radiator, and the Lithium cooled incore thermionic reactor with heat pipe radiator.

A salient effect of density on the dynamics of nonaqueous electrolytes.

PubMed

Han, Sungho

2017-04-24

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Lithium ion conducting electrolytes

DOEpatents

Angell, C. Austen; Liu, Changle

1996-01-01

A liquid, predominantly lithium-conducting, ionic electrolyte having exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature, and comprising the lithium salts selected from the group consisting of the thiocyanate, iodide, bromide, chloride, perchlorate, acetate, tetrafluoroborate, perfluoromethane sulfonate, perfluoromethane sulfonamide, tetrahaloaluminate, and heptahaloaluminate salts of lithium, with or without a magnesium-salt selected from the group consisting of the perchlorate and acetate salts of magnesium. Certain of the latter embodiments may also contain molecular additives from the group of acetonitrile (CH.sub.3 CN) succinnonitrile (CH.sub.2 CN).sub.2, and tetraglyme (CH.sub.3 --O--CH.sub.2 --CH.sub.2 --O--).sub.2 (or like solvents) solvated to a Mg.sup.+2 cation to lower the freezing point of the electrolyte below room temperature. Other particularly useful embodiments contain up to about 40, but preferably not more than about 25, mol percent of a long chain polyether polymer dissolved in the lithium salts to provide an elastic or rubbery solid electrolyte of high ambient temperature conductivity and exceptional 100.degree. C. conductivity. Another embodiment contains up to about but not more than 10 mol percent of a molecular solvent such as acetone.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

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

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Lithium ion conducting electrolytes

DOEpatents

Angell, C.A.; Liu, C.

1996-04-09

A liquid, predominantly lithium-conducting, ionic electrolyte is described having exceptionally high conductivity at temperatures of 100 C or lower, including room temperature, and comprising the lithium salts selected from the group consisting of the thiocyanate, iodide, bromide, chloride, perchlorate, acetate, tetrafluoroborate, perfluoromethane sulfonate, perfluoromethane sulfonamide, tetrahaloaluminate, and heptahaloaluminate salts of lithium, with or without a magnesium-salt selected from the group consisting of the perchlorate and acetate salts of magnesium. Certain of the latter embodiments may also contain molecular additives from the group of acetonitrile (CH{sub 3}CN), succinnonitrile (CH{sub 2}CN){sub 2}, and tetraglyme (CH{sub 3}--O--CH{sub 2}--CH{sub 2}--O--){sub 2} (or like solvents) solvated to a Mg{sup +2} cation to lower the freezing point of the electrolyte below room temperature. Other particularly useful embodiments contain up to about 40, but preferably not more than about 25, mol percent of a long chain polyether polymer dissolved in the lithium salts to provide an elastic or rubbery solid electrolyte of high ambient temperature conductivity and exceptional 100 C conductivity. Another embodiment contains up to about but not more than 10 mol percent of a molecular solvent such as acetone. 2 figs.

Hybrid electrolytes for lithium metal batteries

NASA Astrophysics Data System (ADS)

Keller, Marlou; Varzi, Alberto; Passerini, Stefano

2018-07-01

This perspective article discusses the most recent developments in the field of hybrid electrolytes, here referred to electrolytes composed of two, well-defined ion-conducting phases, for high energy density lithium metal batteries. The two phases can be both solid, as e.g., two inorganic conductors or one inorganic and one polymer conductor, or, differently, one liquid and one inorganic conductor. In this latter case, they are referred as quasi-solid hybrid electrolytes. Techniques for the appropriate characterization of hybrid electrolytes are discussed emphasizing the importance of ionic conduction and interfacial properties. On this view, multilayer systems are also discussed in more detail. Investigations on Lewis acid-base interactions, activation energies for lithium-ion transfer between the phases, and the formation of an interphase between the components are reviewed and analyzed. The application of different hybrid electrolytes in lithium metal cells with various cathode compositions is also discussed. Fabrication methods for the feasibility of large-scale applications are briefly analyzed and different cell designs and configurations, which are most suitable for the integration of hybrid electrolytes, are determined. Finally, the specific energy of cells containing different hybrid electrolytes is estimated to predict possible enhancement in energy with respect to the current lithium-ion battery technology.

Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries

NASA Astrophysics Data System (ADS)

Armstrong, A. Robert; Bruce, Peter G.

1996-06-01

RECHARGEABLE lithium batteries can store more than twice as much energy per unit weight and volume as other rechargeable batteries1,2. They contain lithium ions in an electrolyte, which shuttle back and forth between, and are intercalated by, the electrode materials. The first commercially successful rechargeable lithium battery3, introduced by the Sony Corporation in 1990, consists of a carbon-based negative electrode, layered LiCoO2 as the positive electrode, and a non-aqueous liquid electrolyte. The high cost and toxicity of cobalt compounds, however, has prompted a search for alternative materials that intercalate lithium ions. One such is LiMn2O4, which has been much studied as a positive electrode material4-7 the cost of manganese is less than 1% of that of cobalt, and it is less toxic. Here we report the synthesis and electrochemical performance of a new material, layered LiMnO2, which is structurally analogous to LiCoO2. The charge capacity of LiMnO2 (~270mAhg-1) compares well with that of both LiCoO2 and LiMn2O4, and preliminary results indicate good stability over repeated charge-discharge cycles.

A salient effect of density on the dynamics of nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Han, Sungho

2017-04-01

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

DOE PAGES

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua; ...

2018-04-24

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Magnetic diagnostics for equilibrium reconstructions with eddy currents on the lithium tokamak experiment

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

Schmitt, J. C., E-mail: jschmitt@pppl.gov; Lazerson, S.; Majeski, R.

2014-11-15

The Lithium Tokamak eXperiment is a spherical tokamak with a close-fitting low-recycling wall composed of thin lithium layers evaporated onto a stainless steel-lined copper shell. Long-lived non-axisymmetric eddy currents are induced in the shell and vacuum vessel by transient plasma and coil currents and these eddy currents influence both the plasma and the magnetic diagnostic signals that are used as constraints for equilibrium reconstruction. A newly installed set of re-entrant magnetic diagnostics and internal saddle flux loops, compatible with high-temperatures and lithium environments, is discussed. Details of the axisymmetric (2D) and non-axisymmetric (3D) treatments of the eddy currents and themore » equilibrium reconstruction are presented.« less

Vented target elements for use in an isotope-production reactor. [LMFBR

DOEpatents

Cawley, W.E.; Omberg, R.P.

1982-08-19

A method is described for producing tritium gas in a fast breeder reactor cooled with liquid metal. Lithium target material is placed in pins equipped with vents, and tritium gas is recovered from the coolant.

Assemblies with both target and fuel pins in an isotope-production reactor

DOEpatents

Cawley, W.E.; Omberg, R.P.

1982-08-19

A method is described for producing tritium in a fast breeder reactor cooled with liquid metal. Lithium target material is placed in pins adjacent to fuel pins in order to increase the tritium production rate.

Fluorinated phosphazene co-solvents for improved thermal and safety performance in lithium-ion battery electrolytes

NASA Astrophysics Data System (ADS)

Rollins, Harry W.; Harrup, Mason K.; Dufek, Eric J.; Jamison, David K.; Sazhin, Sergiy V.; Gering, Kevin L.; Daubaras, Dayna L.

2014-10-01

The safety of lithium-ion batteries is coming under increased scrutiny as they are being adopted for large format applications especially in the vehicle transportation industry and for grid-scale energy storage. The primary short-comings of lithium-ion batteries are the flammability of the liquid electrolyte and sensitivity to high voltage and elevated temperatures. We have synthesized a series of non-flammable fluorinated phosphazene liquids and blended them with conventional carbonate solvents. While the use of these phosphazenes as standalone electrolytes is highly desirable, they simply do not satisfy all of the many requirements that must be met such as high LiPF6 solubility and low viscosity, thus we have used them as additives and co-solvents in blends with typical carbonates. The physical and electrochemical properties of the electrolyte blends were characterized, and then the blends were used to build 2032-type coin cells. We have evaluated the performance of the electrolytes by determining the physical properties, thermal stability, electrochemical window, cell cycling data, and the ability to form solid electrolyte interphase (SEI) films. This paper presents our most recent results on a new series of fluorinated cyclic phosphazene trimers, the FM series, which has exhibited numerous beneficial effects on battery performance, lifetimes, and safety aspects.

An Integrated Command and Control Architecture Concept for Unmanned Systems in the Year 2030

DTIC Science & Technology

2010-06-01

98  3.6.4.3.  Lithium Iron Phosphate LiFePO4 ......................................99  3.6.4.4.  Future Battery Developments...Iron Phosphate LiFePO4 Lithium Iron Phosphate is a variation in the chemistry of lithium ion batteries. General electric Battery company research...LCS Littoral Combat Ship LD/HD Low Density/High Demand LiFePO4 Lithium Iron Phosphate LOC Lines of Communication LOE Limited Objective Experiment

Compatibility of lithium plasma-facing surfaces with high edge temperatures in the Lithium Tokamak Experiment (LTX)

NASA Astrophysics Data System (ADS)

Majeski, Dick

2016-10-01

High edge electron temperatures (200 eV or greater) have been measured at the wall-limited plasma boundary in the Lithium Tokamak eXperiment (LTX). High edge temperatures, with flat electron temperature profiles, are a long-predicted consequence of low recycling boundary conditions. The temperature profile in LTX, measured by Thomson scattering, varies by as little as 10% from the plasma axis to the boundary, determined by the lithium-coated high field-side wall. The hydrogen plasma density in the outer scrape-off layer is very low, 2-3 x 1017 m-3 , consistent with a low recycling metallic lithium boundary. The plasma surface interaction in LTX is characterized by a low flux of high energy protons to the lithium PFC, with an estimated Debye sheath potential approaching 1 kV. Plasma-material interactions in LTX are consequently in a novel regime, where the impacting proton energy exceeds the peak in the sputtering yield for the lithium wall. In this regime, further increases in the edge temperature will decrease, rather than increase, the sputtering yield. Despite the high edge temperature, the core impurity content is low. Zeff is 1.2 - 1.5, with a very modest contribution (<0.1) from lithium. So far experiments are transient. Gas puffing is used to increase the plasma density. After gas injection stops, the discharge density is allowed to drop, and the edge is pumped by the low recycling lithium wall. An upgrade to LTX which includes a 35A, 20 kV neutral beam injector to provide core fueling to maintain constant density, as well as auxiliary heating, is underway. Two beam systems have been loaned to LTX by Tri Alpha Energy. Additional results from LTX, as well as progress on the upgrade - LTX- β - will be discussed. Work supported by US DOE contracts DE-AC02-09CH11466 and DE-AC05-00OR22725.

Novel, Solvent-Free, Single Ion Conductive Polymer Electrolytes

DTIC Science & Technology

2008-01-20

liquid oligomeric analogue PEODME (ε = 8, dioxane:CH3CN mass ratio 48:7). The choice of the solvent mixture was a compromise between the...trifluoride – a derivative of Lewis acid properties. An increase in the degree of dissociation, decrease in the share of ionic associates and increase in...diphenylphosphinate this product is a solid, and in reaction with lithium diphenylphosphate the second fraction is a viscous, light-brown liquid , and

Fabrication methods for low impedance lithium polymer electrodes

DOEpatents

Chern, T.S.; MacFadden, K.O.; Johnson, S.L.

1997-12-16

A process is described for fabricating an electrolyte-electrode composite suitable for high energy alkali metal battery that includes mixing composite electrode materials with excess liquid, such as ethylene carbonate or propylene carbonate, to produce an initial formulation, and forming a shaped electrode therefrom. The excess liquid is then removed from the electrode to compact the electrode composite which can be further compacted by compression. The resulting electrode exhibits at least a 75% lower resistance.

Fabrication methods for low impedance lithium polymer electrodes

DOEpatents

Chern, Terry Song-Hsing; MacFadden, Kenneth Orville; Johnson, Steven Lloyd

1997-01-01

A process for fabricating an electrolyte-electrode composite suitable for high energy alkali metal battery that includes mixing composite electrode materials with excess liquid, such as ethylene carbonate or propylene carbonate, to produce an initial formulation, and forming a shaped electrode therefrom. The excess liquid is then removed from the electrode to compact the electrode composite which can be further compacted by compression. The resulting electrode exhibits at least a 75% lower resistance.

Volatilization and Thermal Decomposition Mechanisms of Room-Temperature Ionic Liquids (PRE-PRINT)

DTIC Science & Technology

2017-03-07

Huang, X. J. & Chen, L. Q. “Novel room temperature molten salt electrolyte based on LiTFSI and acetamide for lithium batteries .” Electrochemistry...organic compounds (VOCs) used as industrial solvents with involatile liquids. RTILs also show promise for applications in fuel cells, batteries , solar...indicated that volatilization of these species occurs as a single ion pair. Recent ALS studies on the photoionization of other 1- alkyl-3

Using liquid desiccant as a regenerable filter for capturing and deactivating contaminants

DOEpatents

Slayzak, Steven J.; Anderson, Ren S.; Judkoff, Ronald D.; Blake, Daniel M.; Vinzant, Todd B.; Ryan, Joseph P.

2007-12-11

A method, and systems for implementing such method, for purifying and conditioning air of weaponized contaminants. The method includes wetting a filter packing media with a salt-based liquid desiccant, such as water with a high concentration of lithium chloride. Air is passed through the wetted filter packing media and the contaminants in are captured with the liquid desiccant while the liquid desiccant dehumidifies the air. The captured contaminants are then deactivated in the liquid desiccant, which may include heating the liquid desiccant. The liquid desiccant is regenerated by applying heat to the liquid desiccant and then removing moisture. The method includes repeating the wetting with the regenerated liquid desiccant which provides a regenerable filtering process that captures and deactivates contaminants on an ongoing basis while also conditioning the air. The method may include filtration effectiveness enhancement by electrostatic or inertial means.

Investigation of lithium PFC surface characteristics and low recycling at LTX/LTX-Beta

NASA Astrophysics Data System (ADS)

Maan, Anurag; Kaita, Robert; Elliott, Drew; Boyle, Dennis; Majeski, Richard; Donovan, David; Buzi, Luxherta; Koel, Bruce E.; Biewer, Theodore M.

2017-10-01

Lithium coatings on high-Z PFCs at LTX have led to improved plasma performance. The initial hypothesis was that lithium retains hydrogen by forming lithium hydride and thereby enabling low recycling in LTX. However, recent in-vacuo measurements indicate the presence of lithium oxide in deposited lithium coatings. Improved plasma performance continued to be observed in the presence of lithium oxide. These observations raise questions like what is the nature of the lithium oxide surface, whether the PFC is an amorphous mixture of lithium and lithium oxide or something more ordered like a lithium oxide layer growing on top of lithium, and whether lithium oxide is responsible for any retention of hydrogen from the plasma. To investigate the mechanism by which the LTX PFC might be responsible for low recycling, we discuss the results of deuterium retention measurements using NRA/RBS and sample characterization using high resolution XPS (HR-XPS) in bulk lithium samples. Baseline HR-XPS scans indicate the presence of Lithium Oxide on sputtered lithium samples. Status of related planned experiments at LTX- β will also be discussed. This work was supported by the US. D.O.E. contract DE-AC05-00OR22725 and DE-AC02-09CH11466. BEK acknowledges support of this work by the U.S. DOE, Office of Science/FES under Award Number DE-SC0012890.

Engineering experimental program on the effects of near-space radiation on lithium doped solar cells

NASA Technical Reports Server (NTRS)

1971-01-01

The results of an experimental evaluation of the real-time degradation characteristics of lithium-diffused silicon solar cells are reported. A strontium-90 radioisotope was used for simulation of a typical earth-orbital electron environment. The experiment was performed in an ion pump vacuum chamber with samples maintained at -50, +20, +50, and +80 C. Samples were illuminated during the 6-month exposure run with solar cell 1-5 characteristics measured periodically in situ. This 6-month exposure corresponded to a 1 MeV equivalent fluence of approximately 10 to the 14th power electrons/sq cm. Several types of lithium cells were irradiatied and compared directly with conventional N/P cells. The best lithium cells compared favorably with N/P cells, particularly at the higher test temperatures. With a slight improvement of initial performance characteristics, lithium cells appear feasible for 5 to 10 year missions at synchronous altitude. Based on the reported results and those of other irradiation experiments, lithium cells would appear to be superior to N/P cells in proton-dominated earth-orbital environments. Another important conclusion of the effort was that illuminated/loaded cells degrade more rapidly than do dark/unloaded cells. The irradiation experiment provided data of high quality with a high degree of confidence because of the experimental and statistical analysis techniques utilized.

Fuel pins with both target and fuel pellets in an isotope-production reactor

DOEpatents

Cawley, W.E.; Omberg, R.P.

1982-08-19

A method is described for producing tritium in a fast breeder reactor cooled with liquid metal. Lithium target pellets are placed in close contact with fissile fuel pellets in order to increase the tritium production rate.

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

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

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

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

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.

Hierarchical Carbon with High Nitrogen Doping Level: A Versatile Anode and Cathode Host Material for Long-Life Lithium-Ion and Lithium-Sulfur Batteries.

PubMed

Reitz, Christian; Breitung, Ben; Schneider, Artur; Wang, Di; von der Lehr, Martin; Leichtweiss, Thomas; Janek, Jürgen; Hahn, Horst; Brezesinski, Torsten

2016-04-27

Nitrogen-rich carbon with both a turbostratic microstructure and meso/macroporosity was prepared by hard templating through pyrolysis of a tricyanomethanide-based ionic liquid in the voids of a silica monolith template. This multifunctional carbon not only is a promising anode candidate for long-life lithium-ion batteries but also shows favorable properties as anode and cathode host material owing to a high nitrogen content (>8% after carbonization at 900 °C). To demonstrate the latter, the hierarchical carbon was melt-infiltrated with sulfur as well as coated by atomic layer deposition (ALD) of anatase TiO2, both of which led to high-quality nanocomposites. TiO2 ALD increased the specific capacity of the carbon while maintaining high Coulombic efficiency and cycle life: the composite exhibited stable performance in lithium half-cells, with excellent recovery of low rate capacities after thousands of cycles at 5C. Lithium-sulfur batteries using the sulfur/carbon composite also showed good cyclability, with reversible capacities of ∼700 mA·h·g(-1) at C/5 and without obvious decay over several hundred cycles. The present results demonstrate that nitrogen-rich carbon with an interconnected multimodal pore structure is very versatile and can be used as both active and inactive electrode material in high-performance lithium-based batteries.

Method and system to directly produce electrical power within the lithium blanket region of a magnetically confined, deuterium-tritium (DT) fueled, thermonuclear fusion reactor

DOEpatents

Woolley, Robert D.

1999-01-01

A method for integrating liquid metal magnetohydrodynamic power generation with fusion blanket technology to produce electrical power from a thermonuclear fusion reactor located within a confining magnetic field and within a toroidal structure. A hot liquid metal flows from a liquid metal blanket region into a pump duct of an electromagnetic pump which moves the liquid metal to a mixer where a gas of predetermined pressure is mixed with the pressurized liquid metal to form a Froth mixture. Electrical power is generated by flowing the Froth mixture between electrodes in a generator duct. When the Froth mixture exits the generator the gas is separated from the liquid metal and both are recycled.

Transmission electron microscopy of polymer blends and block copolymers

NASA Astrophysics Data System (ADS)

Gomez, Enrique Daniel

Transmission electron microscopy (TEM) of soft matter is a field that warrants further investigation. Developments in sample preparation, imaging and spectroscopic techniques could lead to novel experiments that may further our understanding of the structure and the role structure plays in the functionality of various organic materials. Unlike most hard materials, TEM of organic molecules is limited by the amount of radiation damage the material can withstand without changing its structure. Despite this limitation, TEM has been and will be a powerful tool to study polymeric materials and other soft matter. In this dissertation, an introduction of TEM for polymer scientists is presented. The fundamentals of interactions of electrons with matter are described using the Schrodinger wave equation and scattering cross-sections to fully encompass coherent and incoherent scattering. The intensity, which is the product of the wave function and its complex conjugate, shows no perceptible change due to the sample. Instead, contrast is generated through the optical system of the microscope by removing scattered electrons or by generating interference due to material-induced phase changes. Perhaps the most challenging aspect of taking TEM images, however, is sample preparation, because TEM experiments require materials with approximately 50 nm thickness. Although ultramicrotomy is a well-established powerful tool for preparing biological and polymeric sections for TEM, the development of cryogenic Focused Ion Beam may enable unprecedented cross-sectional TEM studies of polymer thin films on arbitrary substrates with nanometer precision. Two examples of TEM experiments of polymeric materials are presented. The first involves quantifying the composition profile across a lamellar phase obtained in a multicomponent blend of saturated poly(butadiene) and poly(isobutylene), stabilized by a saturated poly(butadiene) copolymer serving as a surfactant, using TEM and self-consistent field theory (SCFT). The liquid-like nature of this system at room temperature makes traditional staining methods for the enhancement of contrast ineffective. As an alternative, we take advantage of the large inelastic scattering cross-section of soft materials to generate contrast in zero-loss TEM images. Independent spatially resolved thickness measurements enable quantification of electron scattering. This enabled a comparison between the TEM data and predictions based on SCFT without any adjustable parameters. The second example involves the utilization of energy-filtered transmission electron microscopy (EFTEM) to compute elemental maps by taking advantage of ionization events. Elemental mapping of lithium is used to determine the distribution of salt in nanostructured poly(styrene-block-ethylene oxide) (SEO) copolymer/lithium salt electrolytes. Surprisingly, the concentration of lithium within a poly(ethylene oxide) (PEO) domain is found to be inhomogeneous; the salt is localized to the middle of the channels. Self-consistent field theory simulations suggest that localization of lithium is due to chain stretching at the interface, which increases with molecular weight. EFTEM and SCFT results show that the segregation of lithium salt to the middle of the PEO lamellae is greater for higher molecular weight polymers. This is correlated with the ionic conductivity of the copolymer electrolyte, which is found to show a higher conductivity for thinner lithium lamellae.

Relationship between vomiting and taste aversion learning in the ferret: studies with ionizing radiation, lithium chloride, and amphetamine.

PubMed

Rabin, B M; Hunt, W A

1992-09-01

The relationship between emesis and taste aversion learning was studied in ferrets (Mustela putorius furo) following exposure to ionizing radiation (50-200 cGy) or injection of lithium chloride (1.5-3.0 mEq/kg, ip). When 10% sucrose or 0.1% saccharin was used as the conditioned stimulus, neither unconditioned stimulus produced a taste aversion, even when vomiting was produced by the stimulus (Experiments 1 and 2). When a canned cat food was used as the conditioned stimulus, lithium chloride, but not ionizing radiation, produced a taste aversion (Experiment 3). Lithium chloride was effective in producing a conditioned taste aversion when administration of the toxin was delayed by up to 90 min following the ingestion of the canned cat food, indicating that the ferrets are capable of showing long-delay learning (Experiment 4). Experiment 5 examined the capacity of amphetamine, which is a qualitatively different stimulus than lithium chloride or ionizing radiation, to produce taste aversion learning in rats and cats as well as in ferrets. Injection of amphetamine (3 mg/kg, ip) produced a taste aversion in rats and cats but not in ferrets which required a higher dose (> 5 mg/kg). The results of these experiments are interpreted as indicating that, at least for the ferret, there is no necessary relationship between toxin-induced illness and the acquisition of a CTA and that gastrointestinal distress is not a sufficient condition for CTA learning.

Non-aqueous primary cell

NASA Astrophysics Data System (ADS)

James, S. D.; Smith, P. H.; Oneill, K. M.; Wilson, M. H.

1986-05-01

This patent application relates to electrochemical cells and especially to high-energy, liquid cathode, non-aqueous lithium electrochemical cells free from highly toxic materials. A non-aqueous lithium electrochemical cell is described which includes a halocarbon cathode depolarizer which is 1,2-dichloroethane, 1.1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloro-1,1-difluoroethane or mixtures thereof and a cathode catalyst which is copper, rhodium, palladium, cobalt phthalocyanine, nickel phthalocyanine, iron phthalocyanine, a cobalt tetraaza-(14)-annulene, a nickel tetraaza-(14)-annulene, a iron tetraaza-(14)-annulene, a cobalt porphyrin, a nickel porphyrin, a iron porphyrin, or a mixture thereof.

Gel polymer electrolyte for lithium-ion batteries comprising cyclic carbonate moieties

NASA Astrophysics Data System (ADS)

Tillmann, S. D.; Isken, P.; Lex-Balducci, A.

2014-12-01

A polymer system based on oligo (ethylene glycol) methyl ether methacrylate (OEGMA) and cyclic carbonate methacrylate (CCMA) was chosen as matrix to realize high-performance gel polymer electrolytes due to the fact that both monomers are able to interact with the liquid electrolyte, thus, retaining it inside the matrix. Additionally, OEGMA enables high flexibility, while CCMA provides mechanical stability. The polymer displays a high thermal stability up to 200 °C and a glass transition temperature below room temperature (5 °C) allowing an easy handling of the obtained films. By immobilizing the liquid electrolyte 1 M LiPF6 in EC:DMC 1:1 w:w in the polymer host a gel polymer electrolyte with a high conductivity of 2.3 mS cm-1 at 25 °C and a stable cycling behavior with high capacities and efficiencies in Li(Ni1/3Co1/3Mn1/3)O2 (NCM)/graphite full cells is obtained. The investigated gel polymer electrolyte is identified as promising electrolyte for lithium-ion batteries, because it combines good electrochemical properties comparable to that of liquid electrolytes with the safety advantage that no leakage of the flammable electrolyte solvents can occur.

Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid.

PubMed

Yang, Chunpeng; Fu, Kun; Zhang, Ying; Hitz, Emily; Hu, Liangbing

2017-09-01

High-energy lithium-metal batteries are among the most promising candidates for next-generation energy storage systems. With a high specific capacity and a low reduction potential, the Li-metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li-metal anodes. Recent studies have shown that the performance and safety of Li-metal anodes can be significantly improved via organic electrolyte modification, Li-metal interface protection, Li-electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid-state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li-metal batteries. Inspired by the bright prospects of solid Li-metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li-metal batteries, such as low ionic conductivity of the electrolyte and Li-electrolyte interfacial problems. Here, the approaches to protect Li-metal anodes from liquid batteries to solid-state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li-metal anodes are discussed to facilitate the practical application of Li-metal batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixtures of glyme and aprotic-protic ionic liquids as electrolytes for energy storage devices

NASA Astrophysics Data System (ADS)

Stettner, T.; Huang, P.; Goktas, M.; Adelhelm, P.; Balducci, A.

2018-05-01

Ionic liquids (ILs) have been proven to be promising electrolytes for electrochemical energy storage devices such as supercapacitors and lithium ion batteries. In the last years, due to deficiency in storage of lithium on earth, innovative systems, such as sodium-based devices, attracted considerable attention. IL-based electrolytes have been proposed also as electrolytes for these devices. Nevertheless, in the case of these systems, the advantages and limits of IL-based electrolytes need to be further investigated. In this work we report an investigation about the chemical-physical properties of mixtures containing bis(2-methoxyethyl)ether diglyme (2G), which is presently considered as one of the most interesting solvents for sodium-based devices, and the ionic liquids 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) and 1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PyrH4TFSI). The conductivities, viscosities, and densities of several mixtures of 2G and these ILs have been investigated. Furthermore, their impact on the electrochemical behaviour of activated carbon composite electrodes has been considered. The results of this investigation indicate that these mixtures are promising electrolytes for the realization of advanced sodium-based devices.

The melting point of lithium: an orbital-free first-principles molecular dynamics study

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

Chen, Mohan; Hung, Linda; Huang, Chen

2013-08-25

The melting point of liquid lithium near zero pressure is studied with large-scale orbital-free first-principles molecular dynamics (OF-FPMD) in the isobaric-isothermal ensemble. Here, we adopt the Wang-Govind-Carter (WGC) functional as our kinetic energy density functional (KEDF) and construct a bulk-derived local pseudopotential (BLPS) for Li. Our simulations employ both the ‘heat-until-melts’ method and the coexistence method. We predict 465 K as an upper bound of the melting point of Li from the ‘heat-until-melts’ method, while we predict 434 K as the melting point of Li from the coexistence method. These values compare well with an experimental melting point of 453more » K at zero pressure. Furthermore, we calculate a few important properties of liquid Li including the diffusion coefficients, pair distribution functions, static structure factors, and compressibilities of Li at 470 K and 725 K in the canonical ensemble. This theoretically-obtained results show good agreement with known experimental results, suggesting that OF-FPMD using a non-local KEDF and a BLPS is capable of accurately describing liquid metals.« less

Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bennett, William R.; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

2014-01-01

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

Single-Wall Carbon Nanotube Anodes for Lithium Cells

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Raffaelle, Ryne; Gennett, Tom; Kumta, Prashant; Maranchi, Jeff; Heben, Mike

2006-01-01

In recent experiments, highly purified batches of single-wall carbon nanotubes (SWCNTs) have shown promise as superior alternatives to the graphitic carbon-black anode materials heretofore used in rechargeable thin-film lithium power cells. The basic idea underlying the experiments is that relative to a given mass of graphitic carbon-black anode material, an equal mass of SWCNTs can be expected to have greater lithium-storage and charge/discharge capacities. The reason for this expectation is that whereas the microstructure and nanostructure of a graphitic carbon black is such as to make most of the interior of the material inaccessible for intercalation of lithium, a batch of SWCNTs can be made to have a much more open microstructure and nanostructure, such that most of the interior of the material is accessible for intercalation of lithium. Moreover, the greater accessibility of SWCNT structures can be expected to translate to greater mobilities for ion-exchange processes and, hence, an ability to sustain greater charge and discharge current densities.

Liquid micro-lens array activated by selective electrowetting on lithium niobate substrates.

PubMed

Grilli, S; Miccio, L; Vespini, V; Finizio, A; De Nicola, S; Ferraro, Pietro

2008-05-26

Lens effect was obtained in an open microfluidic system by using a thin layer of liquid on a polar electric crystal like LiNbO3. An array of liquid micro-lenses was generated by electrowetting effect in pyroelectric periodically poled crystals. Compared to conventional electrowetting devices, the pyroelectric effect allowed to have an electrode-less and circuit-less configuration. An interferometric technique was used to characterize the curvature of the micro-lenses and the corresponding results are presented and discussed. The preliminary results concerning the imaging capability of the micro-lens array are also reported.

Method of making electrodes for electrochemical cell. [Li-Al alloy

DOEpatents

Kaun, T.D.; Kilsdonk, D.J.

1981-07-29

A method is described for making an electrode for an electrochemical cell in which particulate electrode-active material is mixed with a liquid organic carrier chemically inert with respect to the electrode-active material, mixing the liquid carrier to form an extrudable slurry. The liquid carrier is present in an amount of from about 10 to about 50% by volume of the slurry, and then the carrier is removed from the slurry leaving the electrode-active material. The method is particularly suited for making a lithium-aluminum alloy negative electrode for a high-temperature cell.

Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries

DOE PAGES

Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.; ...

2016-03-31

Fluorinated carbonate solvents are pursued as liquid electrolytes for high-voltage Li-ion batteries. We report aggregation of [Li +(FEC) 3] n polymer species from fluoroethylene carbonate containing electrolytes and scrutinized the causes for this behavior.

Continuous production of tritium in an isotope-production reactor with a separate circulation system

DOEpatents

Cawley, W.E.; Omberg, R.P.

1982-08-19

A method is described for producing tritium in a fast breeder reactor cooled with liquid metal. Lithium is allowed to flow through the reactor in separate loops in order to facilitate the production and removal of tritium.

Liquid-like ionic conduction in solid lithium and sodium monocarba- closo-decaborates near or at room temperature

DOE PAGES

Tang, Wan Si; Matsuo, Motoaki; Wu, Hui; ...

2016-02-05

Both LiCB 9H 10 and NaCB 9H 10 exhibit liquid-like cationic conductivities (≥0.03 S cm –1) in their disordered hexagonal phases near or at room temperature. Furthermore, these unprecedented conductivities and favorable stabilities enabled by the large pseudoaromatic polyhedral anions render these materials in their pristine or further modified forms as promising solid electrolytes in next-generation, power devices.

Ground Vehicle Power and Mobility Overview

DTIC Science & Technology

2007-05-30

Program Li-Ion Phosphate (LFP) Cathode Materials Large Format Li-Ion Prismatic Cells and Modules with Integrated Liquid Cooling Integrated Prototype...using porous graphitic material3 4 5 8 5 6 60 W-hr/kg 80-120 W/kg Low Cycle Life LFP cathode Safer Less energetic materials ~ ~ Power Cell 85-120...Thermal Runaway Study Zebra Battery NaNiCl2 (FY08 ATO) Advanced Lead Acid LiFePO4 Cathode Prismatic Lithium-ion batteries and Integrated Liquid Cooling

Separation of Californium from other Actinides

DOEpatents

Mailen, J C; Ferris, L M

1973-09-25

A method is provided for separating californium from a fused fluoride composition containing californium and at least one element selected from the group consisting of plutonium, americium, curium, uranium, thorium, and protactinium which comprises contacting said fluoride composition with a liquid bismuth phase containing sufficient lithium or thorium to effect transfer of said actinides to the bismuth phase and then contacting the liquid bismuth phase with molten LiCl to effect selective transfer of californium to the chloride phase.

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

NASA Astrophysics Data System (ADS)

Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

2002-11-01

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Characterization of microporous separators for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Venugopal, Ganesh; Moore, John; Howard, Jason; Pendalwar, Shekhar

Several properties including porosity, pore-size distribution, thickness value, electrochemical stability and mechanical properties have to be optimized before a membrane can qualify as a separator for a lithium-ion battery. In this paper we present results of characterization studies carried out on some commercially available lithium-ion battery separators. The relevance of these results to battery performance and safety are also discussed. Porosity values were measured using a simple liquid absorption test and gas permeabilities were measured using a novel pressure drop technique that is similar in principle to the Gurley test. For separators from one particular manufacturer, the trend observed in the pressure drop times was found to be in agreement with the Gurley numbers reported by the separator manufacturer. Shutdown characteristics of the separators were studied by measuring the impedance of batteries containing the separators as a function of temperature. Overcharge tests were also performed to confirm that separator shutdown is indeed a useful mechanism for preventing thermal runaway situations. Polyethylene containing separators, in particular trilayer laminates of polypropylene, polyethylene and polypropylene, appear to have the most attractive properties for preventing thermal runaway in lithium ion cells.