Ternary compound electrode for lithium cells

DOEpatents

Raistrick, I.D.; Godshall, N.A.; Huggins, R.A.

1980-07-30

Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and of light weight. One type of lithium-based cell utilizes a molten salt electrolyte and normally is operated in the temperature range of about 350 to 500/sup 0/C. Such high temperature operation accelerates corrosion problems. The present invention provides an electrochemical cell in which lithium is the electroactive species. The cell has a positive electrode which includes a ternary compound generally represented as Li-M-O, wherein M is a transition metal. Corrosion of the inventive cell is considerably reduced.

Ternary compound electrode for lithium cells

DOEpatents

Raistrick, Ian D.; Godshall, Ned A.; Huggins, Robert A.

1982-01-01

Lithium-based cells are promising for applications such as electric vehicles and load-leveling for power plants since lithium is very electropositive and of light weight. One type of lithium-based cell utilizes a molten salt electrolyte and normally is operated in the temperature range of about 350.degree.-500.degree. C. Such high temperature operation accelerates corrosion problems. The present invention provides an electrochemical cell in which lithium is the electroactive species. The cell has a positive electrode which includes a ternary compound generally represented as Li-M-O, wherein M is a transition metal. Corrosion of the inventive cell is considerably reduced.

Semiconductor neutron detector

DOEpatents

Ianakiev, Kiril D [Los Alamos, NM; Littlewood, Peter B [Cambridge, GB; Blagoev, Krastan B [Arlington, VA; Swinhoe, Martyn T [Los Alamos, NM; Smith, James L [Los Alamos, NM; Sullivan, Clair J [Los Alamos, NM; Alexandrov, Boian S [Los Alamos, NM; Lashley, Jason Charles [Santa Fe, NM

2011-03-08

A neutron detector has a compound of lithium in a single crystal form as a neutron sensor element. The lithium compound, containing improved charge transport properties, is either lithium niobate or lithium tantalate. The sensor element is in direct contact with a monitor that detects an electric current. A signal proportional to the electric current is produced and is calibrated to indicate the neutrons sensed. The neutron detector is particularly useful for detecting neutrons in a radiation environment. Such radiation environment may, e.g. include gamma radiation and noise.

The use of lithium compounds for inhibiting alkali-aggregate reaction effects in pavement structures

NASA Astrophysics Data System (ADS)

Zapała-Sławeta, J.; Owsiak, Z.

2018-05-01

Internal corrosion of concrete caused by the reaction of reactive aggregate with sodium and potassium hydroxides from cement is a threat to the durability of concrete pavements. Traditional methods for reducing the negative effects of the reaction include the use of unreactive aggregates, low alkali cements, mineral additives or chemical admixtures, incorporated during mixing. Lowering the relative humidity of the concrete below 80% is another measure for limiting the destructive reaction. The incorporation of lithium compounds, in particular lithium nitrate and lithium hydroxide, to the concrete mix is a method of limiting alkali-silica reaction effects. The challenge is to reduce the negative effects of aggregate reactivity in members in which the reaction has occurred because the aggregate happened to be reactive. The paper presents ways of limiting the deterioration of ASR-affected concrete in road pavements and other forms of transportation infrastructure, mainly through the use of lithium compounds, i.e. lithium nitrate. Impregnation methods that allow the penetration of lithium ions into the concrete structure were characterized, as was the effectiveness of the solutions applied.

Synthesis of tritium breeder ceramics from metallic lithium

NASA Astrophysics Data System (ADS)

Knitter, R.; Kolb, M. H. H.; Odemer, C.

2012-01-01

For the fabrication of Li-6 enriched ceramic breeder materials for ITER, the availability of Li-6 enriched compounds is limited, and metallic Li-6 is the most widely available compound. As metallic lithium cannot be used directly in ceramic fabrication processes, we investigated different syntheses to obtain lithium orthosilicate or lithium metatitanate directly from molten lithium. In exothermic reactions of molten lithium with silicon, silica, or titania, several intermediate or precursor phases were observed under argon that could easily be transformed to the desired ceramic phases by a subsequent heat treatment under air. The reaction steps and the resulting phases were studied by differential scanning calorimetry and X-ray diffractometry. The synthesis from lithium and silicon seems to be especially suited for the production of larger quantities and has the advantage that silicon is available with a very high grade of purity.

48 CFR 908.7121 - Special materials.

Code of Federal Regulations, 2013 CFR

2013-10-01

... reporting. (c) Lithium. Lithium is available from Y-12 at no cost other than normal packing, handling, and... procurement of lithium compounds from any other source. [77 FR 74387, Dec. 14, 2012] ...

48 CFR 908.7121 - Special materials.

Code of Federal Regulations, 2014 CFR

2014-10-01

... reporting. (c) Lithium. Lithium is available from Y-12 at no cost other than normal packing, handling, and... procurement of lithium compounds from any other source. [77 FR 74387, Dec. 14, 2012] ...

A Comparative Study of Structural Stability and Mechanical and Optical Properties of Fluorapatite (Ca5(PO4)3F) and Lithium Disilicate (Li2Si2O5) Components Forming Dental Glass-Ceramics: First Principles Study

NASA Astrophysics Data System (ADS)

Biskri, Z. E.; Rached, H.; Bouchear, M.; Rached, D.; Aida, M. S.

2016-10-01

The aim of this paper is a comparative study of structural stability and mechanical and optical properties of fluorapatite (FA) (Ca5(PO4)3F) and lithium disilicate (LD) (Li2Si2O5), using the first principles pseudopotential method based on density functional theory (DFT) within the generalized gradient approximation (GGA). The stability of fluorapatite and lithium disilicate compounds has been evaluated on the basis of their formation enthalpies. The results show that fluorapatite is more energetically stable than lithium disilicate. The independent elastic constants and related mechanical properties, including bulk modulus ( B), shear modulus ( G), Young's modulus ( E) and Poisson's ratio ( ν) as well as the Vickers hardness ( H v), have been calculated for fluorapatite compound and compared with other theoretical and experimental results. The obtained values of the shear modulus, Young's modulus and Vickers hardness are smaller in comparison with those of lithium disilicate compound, implying that lithium disilicate is more rigid than fluorapatite. The brittle and ductile properties were also discussed using B/ G ratio and Poisson's ratio. Optical properties such as refractive index n( ω), extinction coefficient k( ω), absorption coefficient α( ω) and optical reflectivity R( ω) have been determined from the calculations of the complex dielectric function ɛ( ω), and interpreted on the basis of the electronic structures of both compounds. The calculated values of static dielectric constant ɛ 1(0) and static refractive index n(0) show that the Li2Si2O5 compound has larger values compared to those of the Ca5(PO4)3F compound. The results of the extinction coefficient show that Li2Si2O5 compound exhibits a much stronger ultraviolet absorption. According to the absorption and reflectivity spectra, we inferred that both compounds are theoretically the best visible and infrared transparent materials.

48 CFR 908.7121 - Special materials.

Code of Federal Regulations, 2011 CFR

2011-10-01

...) Lithium. Lithium is available at no cost other than normal packing, handling, and shipping charges from... to procurement of lithium compounds from any other source. [54 FR 27646, June 30, 1989, as amended at...

48 CFR 908.7121 - Special materials.

Code of Federal Regulations, 2012 CFR

2012-10-01

...) Lithium. Lithium is available at no cost other than normal packing, handling, and shipping charges from... to procurement of lithium compounds from any other source. [54 FR 27646, June 30, 1989, as amended at...

48 CFR 908.7121 - Special materials.

Code of Federal Regulations, 2010 CFR

2010-10-01

...) Lithium. Lithium is available at no cost other than normal packing, handling, and shipping charges from... to procurement of lithium compounds from any other source. [54 FR 27646, June 30, 1989, as amended at...

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.

Non-aqueous electrolyte for lithium-ion battery

DOEpatents

Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

2014-04-15

The present technology relates to stabilizing additives and electrolytes containing the same for use in electrochemical devices such as lithium ion batteries and capacitors. The stabilizing additives include triazinane triones and bicyclic compounds comprising succinic anhydride, such as compounds of Formulas I and II described herein.

Lithium ethylene dicarbonate identified as the primary product of chemical and electrochemical reduction of EC in 1.2 M LiPF6/EC:EMC electrolyte.

PubMed

Zhuang, Guorong V; Xu, Kang; Yang, Hui; Jow, T Richard; Ross, Philip N

2005-09-22

Lithium ethylene dicarbonate ((CH2OCO2Li)2) was chemically synthesized and its Fourier transform infrared (FTIR) spectrum was obtained and compared with that of surface films formed on Ni after cyclic voltammetry (CV) in 1.2 M lithium hexafluorophosphate (LiPF6)/ethylene carbonate (EC):ethyl methyl carbonate (EMC) (3:7, w/w) electrolyte and on metallic lithium cleaved in-situ in the same electrolyte. By comparison of IR experimental spectra with that of the synthesized compound, we established that the title compound is the predominant surface species in both instances. Detailed analysis of the IR spectrum utilizing quantum chemical (Hartree-Fock) calculations indicates that intermolecular association through O...Li...O interactions is very important in this compound. It is likely that the title compound in the passivation layer has a highly associated structure, but the exact intermolecular conformation could not be established on the basis of analysis of the IR spectrum.

Rechargeable lithium battery for use in applications requiring a low to high power output

DOEpatents

Bates, John B.

1996-01-01

Rechargeable lithium batteries which employ characteristics of thin-film batteries can be used to satisfy power requirements within a relatively broad range. Thin-film battery cells utilizing a film of anode material, a film of cathode material and an electrolyte of an amorphorus lithium phosphorus oxynitride can be connected in series or parallel relationship for the purpose of withdrawing electrical power simultaneously from the cells. In addition, such battery cells which employ a lithium intercalation compound as its cathode material can be connected in a manner suitable for supplying power for the operation of an electric vehicle. Still further, by incorporating within the battery cell a relatively thick cathode of a lithium intercalation compound, a relatively thick anode of lithium and an electrolyte film of lithium phosphorus oxynitride, the battery cell is rendered capable of supplying power for any of a number of consumer products, such as a laptop computer or a cellular telephone.

Rechargeable lithium battery for use in applications requiring a low to high power output

DOEpatents

Bates, John B.

1997-01-01

Rechargeable lithium batteries which employ characteristics of thin-film batteries can be used to satisfy power requirements within a relatively broad range. Thin-film battery cells utilizing a film of anode material, a film of cathode material and an electrolyte of an amorphous lithium phosphorus oxynitride can be connected in series or parallel relationship for the purpose of withdrawing electrical power simultaneously from the cells. In addition, such battery cells which employ a lithium intercalation compound as its cathode material can be connected in a manner suitable for supplying power for the operation of an electric vehicle. Still further, by incorporating within the battery cell a relatively thick cathode of a lithium intercalation compound, a relatively thick anode of lithium and an electrolyte film of lithium phosphorus oxynitride, the battery cell is rendered capable of supplying power for any of a number of consumer products, such as a laptop computer or a cellular telephone.

THE DIFFERENTIAL THERMAL ANALYSIS OF CYANO-TRANSITION METAL COMPLEXES

DTIC Science & Technology

COMPOUNDS, CHROMATES, COBALT COMPOUNDS, CYANIDES, CYANOGEN, DYES, FERRATES , GASES, HEAT, HYDROXIDES, LITHIUM COMPOUNDS, MOLYBDATES, NICKELATES, NITRATES...OXIDATION REDUCTION REACTIONS, POTASSIUM COMPOUNDS, SILVER COMPOUNDS, SODIUM COMPOUNDS, VANADATES

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.

Development and In Situ Characterization of New Electrolyte and Electrode materials for Rechargeable Lithium Batteries

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

Yang, X -Q; Xing, X K; Daroux, M

The object of this project is to develop new electrolyte and cathode materials for rechargeable lithium batteries, especially for lithium ion and lithium polymer batteries. Enhancing performance, reducing cost, and replacing toxic materials by environmentally benign materials, are strategic goals of DOE in lithium battery research. This proposed project will address these goals on two important material studies, namely the new electrolytes and new cathode materials. For the new electrolyte materials, aza based anion receptors as additives, organic lithium salts and plasticizers which have been developed by BNL team under Energy Research programs of DOE, will be evaluated by Gouldmore » for potential use in commercial battery cells. All of these three types of compounds are aimed to enhance the conductivity and lithium transference number of lithium battery electrolytes and reduce the use of toxic salts in these electrolytes. BNL group will be working closely with Gould to further develop these compounds for commercialization. For the cathode material studies, BNL efforts wi U be focused on developing new superior characterization methclds, especially in situ techniques utilize the unique user facility of DOE at BNL, namely the National Synchrotrons Light Source (NSLS). In situ x-ray absorption and x-ray diftlaction spectroscopy will be used to study the relationship between performance and the electronic and structural characteristics of intercalation compounds such as LiNi0 2, LiCo0 2, and LiMn 20 4 spinel. The study will be focused on LiMn 20 4 spinel materials. Gould team will contribute their expertise in choosing the most promising compounds, providing overall performance requirements, and will use the results of this study to guide their procedure for quality control. The knowledge gained through this project will not only benefit Gould and BNL, but will be very valuable to the scientific community in battery research.« less

Surface protected lithium-metal-oxide electrodes

DOEpatents

Thackeray, Michael M.; Kang, Sun-Ho

2016-04-05

A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

The insertion products of 2-picolyl lithium salt with benzonitrile and terephthalonitrile

NASA Astrophysics Data System (ADS)

Zhang, Yihao; Xiao, Xia; Bai, Jianliang; Cao, Wei; Chen, Xia

2018-02-01

Treatment of 2-picoline with BunLi in THF affords its corresponding 2-picolyl lithium salt in a high yield. The insertion of benzonitrile into the Lisbnd C bond of 2-picolyl lithium followed by acidic hydrolysis yields the corresponding β-pyridyl ketone (1), and diketone compounds (2) is obtained from 1 by intermolecular elimination of proton under the base condition. Similarly, the insertion of terephthalonitrile into 2-picolyl lithium leads to a 1,4-phenyl-linked pyridyl-azaalyl dilithium complex 4, followed by acidic hydrolysis yields corresponding 1,4-phenyl-linked dipyridylketone 3. The probable reaction pathway for the formation of 2 has been investigated. Compound 2 and 4 have been characterized by single-crystal X-ray crystallography.

Cyanoethylated compounds as additives in lithium/lithium batteries

DOEpatents

Nagasubramanian, Ganesan

1999-01-01

The power loss of lithium/lithium ion battery cells is significantly reduced, especially at low temperatures, when about 1% by weight of an additive is incorporated in the electrolyte layer of the cells. The usable additives are organic solvent soluble cyanoethylated polysaccharides and poly(vinyl alcohol). The power loss decrease results primarily from the decrease in the charge transfer resistance at the interface between the electrolyte and the cathode.

FMC: Expanding its chemical universe

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

Wood, A.

1992-12-23

With a portfolio ranging from defense systems to gold to food machinery - the source of its name - FMC Corp. (Chicago) ranks as a diversified conglomerate. The company's industrial chemicals operation consists of alkali chemicals, chiefly soda ash and derivatives: peroxygen chemicals, made up of hydrogen peroxide and other peroxygens; and phosphorus chemicals. FMC has about a 30% market share in each of these three. It also includes the Foret (Barcelona) division, part of FMC Europe. Moving lithium into FMC's specialties group reflects the R D-intensive nature of many lithium compounds, explains F. Wyman Morgan, director/group technology for themore » chemical product and specialty chemicals groups. FMC is also involved in collaborative research programs to develop lithium-based batteries and fuel cells. We have a decentralized business-oriented R D focus, Morgan says. The main thrusts in lithium are in developing organolithiums for drug synthesis. FMC also has a major industrial lithium business; it recently added a new butyl lithium unit in Texas and is looking to expand production through the development of lithium deposits in Latin America. But lithium is growing fastest in the downstream areas, says W. Reginald Hall, v.p. and group manager/specialty chemicals group. It has an unbelievable range of uses, he says, including catalytic applications in the pharmaceuticals industry. We are working on lithium compounds that allow you to drop a functional organic group into a molecule in a reliable way.« less

200 Years of Lithium and 100 Years of Organolithium Chemistry

PubMed Central

2018-01-01

The element lithium has been discovered 200 years ago. Due to its unique properties it has emerged to play a vital role in industry, esp. for energy storage, and lithium‐based products and processes support sustainable technological developments. In addition to the many uses of lithium in its inorganic forms, lithium has a rich organometallic chemistry. The development of organometallic chemistry has been hindered by synthetic problems from the start. When Wilhelm Schlenk developed the basic principles to handle and synthesize air‐ and moisture‐sensitive compounds, the road was open to further developments. After more information was available about the stability and solubility of such compounds, they started to play an essential role in other fields of chemistry as alkyl or aryl transfer reagents. PMID:29540939

Uncharged positive electrode composition

DOEpatents

Kaun, Thomas D.; Vissers, Donald R.; Shimotake, Hiroshi

1977-03-08

An uncharged positive-electrode composition contains particulate lithium sulfide, another alkali metal or alkaline earth metal compound other than sulfide, e.g., lithium carbide, and a transition metal powder. The composition along with a binder, such as electrolytic salt or a thermosetting resin is applied onto an electrically conductive substrate to form a plaque. The plaque is assembled as a positive electrode within an electrochemical cell opposite to a negative electrode containing a material such as aluminum or silicon for alloying with lithium. During charging, lithium alloy is formed within the negative electrode and transition metal sulfide such as iron sulfide is produced within the positive electrode. Excess negative electrode capacity over that from the transition metal sulfide is provided due to the electrochemical reaction of the other than sulfide alkali metal or alkaline earth metal compound.

The effect of Li2CO3 substitution on synthesis of LiBOB compounds as salt of electrolyte battery lithium ion

NASA Astrophysics Data System (ADS)

Lestariningsih, Titik; Wigayati, Etty Marty; Sabrina, Qolby; Prihandoko, Bambang; Priyono, Slamet

2018-04-01

Development of the synthesis of LiB(C2O4)2 compounds continues to evolve along with the need for electrolyte salts to support the research of the manufacture of lithium ion batteries. A study had been conducted on the effect of Li2CO3 substitution on the synthesis of LiB(C2O4)2 or LiBOB compounds. LiBOB was a major candidate to replace LiPF6 as a highly toxic lithium battery electrolyte and harmful to human health. Synthesis of Lithium bis(oxalato) borate used powder metallurgy method. The raw materials used are H2C2O4.2H2O, Li2CO3 or LiOH and H2BO3 from Merck Germany products. The materials are mixed with 2: 1: 1 mol ratio until homogeneous. The synthesis of LiBOB refers to previous research, where the heating process was done gradually. The first stage heating is carried out at 120°C for 4 hours, then the next stage heating is carried out at 240°C for 7 hours. The sample variation in this study was to distinguish the lithium source from Li2CO3 and LiOH. Characterization was done by XRD to know the phase formed, FTIR to confirm that functional group of LiB(C2O4)2 compound, SEM to know the morphological structure, and TG/DTA to know the thermal properties. The results of the analysis shows that LiBOB synthesis using Lithium source from Li2CO3 has succeeded to form LiBOB compound with more LiBOB phase composition is 59.1% and 40.9% LiBOB hydrate phase, SEM morphology shows powder consist of elongated round particle porous and similar to LiBOB commercial and show higher thermal stability.

Agile Thermal Management STT-RX: Themophysical Properties of Lithium Nitrate Trihydrate from - 20 degrees C to 80 degrees C (Preprint)

DTIC Science & Technology

2011-12-01

of interest as a thermal energy storage material, due to its large specific and volumetric heats of fusion and its low melting temperature. Here, we...compound to water and octadecane, two other potential thermal energy storage materials. Furthermore, we examine the lithium nitrate-water phase diagram and...lithium nitrate trihydrate-lithium nitrate eutectic point (Hfus = 264 ± 2 J·g-1, Tm = 28.3 °C). 15. SUBJECT TERMS salt hydrate, thermal energy

Mechanically Resilient Polymeric Films Doped with a Lithium Compound

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B. (Inventor); Kinder, James D. (Inventor)

2005-01-01

This invention is a series of mechanically resilient polymeric films, comprising rod-coil block polyimide copolymers, which are doped with a lithium compound providing lithium ion conductivity, that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consists of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

(abstract) Effect of Electrolyte Composition on Carbon Electrode Performance

NASA Technical Reports Server (NTRS)

Huang, C-K.; Surampudi, S.; Shen, D. H.; Halpert, G.

1993-01-01

Rechargeable lithium cells containing lithium foil anodes are reported to have limited cycle life (at 100% DOD) performance and safety problems. These limitations are understood to be due to the high reactivity of elemental Li with the electrolyte and the formation of high surface area Li during cycling. To mitigate these problems, several lithium alloys and lithium intercalation compounds are being investigated as alternate lithium anode materials. Li(sub x)C has been identified as a promising lithium anode material due to its low equivalent weight, low voltage vs. Li, and improved stability towards various electrolytes. In this paper, we report the results of our studies on the electrolyte evaluation for the Li(sub x)C anode.

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

PubMed Central

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-01-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ∼3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries. PMID:28585527

Electrolytic method for the production of lithium using a lithium-amalgam electrode

DOEpatents

Cooper, John F.; Krikorian, Oscar H.; Homsy, Robert V.

1979-01-01

A method for recovering lithium from its molten amalgam by electrolysis of the amalgam in an electrolytic cell containing as a molten electrolyte a fused-salt consisting essentially of a mixture of two or more alkali metal halides, preferably alkali metal halides selected from lithium iodide, lithium chloride, potassium iodide and potassium chloride. A particularly suitable molten electrolyte is a fused-salt consisting essentially of a mixture of at least three components obtained by modifying an eutectic mixture of LiI-KI by the addition of a minor amount of one or more alkali metal halides. The lithium-amalgam fused-salt cell may be used in an electrolytic system for recovering lithium from an aqueous solution of a lithium compound, wherein electrolysis of the aqueous solution in an aqueous cell in the presence of a mercury cathode produces a lithium amalgam. The present method is particularly useful for the regeneration of lithium from the aqueous reaction products of a lithium-water-air battery.

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

NASA Astrophysics Data System (ADS)

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-06-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ~3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries.

High-capacity electrode materials for rechargeable lithium batteries: Li3NbO4-based system with cation-disordered rocksalt structure.

PubMed

Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu; Shiiba, Hiromasa; Ogawa, Masahiro; Nakayama, Keisuke; Ohta, Toshiaki; Endo, Daisuke; Ozaki, Tetsuya; Inamasu, Tokuo; Sato, Kei; Komaba, Shinichi

2015-06-23

Rechargeable lithium batteries have rapidly risen to prominence as fundamental devices for green and sustainable energy development. Lithium batteries are now used as power sources for electric vehicles. However, materials innovations are still needed to satisfy the growing demand for increasing energy density of lithium batteries. In the past decade, lithium-excess compounds, Li2MeO3 (Me = Mn(4+), Ru(4+), etc.), have been extensively studied as high-capacity positive electrode materials. Although the origin as the high reversible capacity has been a debatable subject for a long time, recently it has been confirmed that charge compensation is partly achieved by solid-state redox of nonmetal anions (i.e., oxide ions), coupled with solid-state redox of transition metals, which is the basic theory used for classic lithium insertion materials, such as LiMeO2 (Me = Co(3+), Ni(3+), etc.). Herein, as a compound with further excess lithium contents, a cation-ordered rocksalt phase with lithium and pentavalent niobium ions, Li3NbO4, is first examined as the host structure of a new series of high-capacity positive electrode materials for rechargeable lithium batteries. Approximately 300 mAh ⋅ g(-1) of high-reversible capacity at 50 °C is experimentally observed, which partly originates from charge compensation by solid-state redox of oxide ions. It is proposed that such a charge compensation process by oxide ions is effectively stabilized by the presence of electrochemically inactive niobium ions. These results will contribute to the development of a new class of high-capacity electrode materials, potentially with further lithium enrichment (and fewer transition metals) in the close-packed framework structure with oxide ions.

Ion and gas chromatography mass spectrometry investigations of organophosphates in lithium ion battery electrolytes by electrochemical aging at elevated cathode potentials

NASA Astrophysics Data System (ADS)

Weber, Waldemar; Wagner, Ralf; Streipert, Benjamin; Kraft, Vadim; Winter, Martin; Nowak, Sascha

2016-02-01

The electrochemical aging of commercial non-aqueous lithium hexafluorophosphate (LiPF6)/organic carbonate solvent based lithium ion battery electrolyte has been investigated in view of the formation of ionic and non-ionic alkylated phosphates. Subject was a solvent mixture of ethylene carbonate/ethyl methyl carbonate EC:EMC (1:1, by wt.) with 1 M LiPF6 (LP50 Selectilyte™, BASF). The analysis was carried out by ion chromatography coupled with electrospray ionization mass spectrometry (ESI-MS) for ionic compounds and (headspace) gas chromatography mass spectrometry ((HS)-GC-MS) for non-ionic compounds. The electrochemical aging was performed by galvanostatic charge/discharge cycling and potentiostatic experiments with LiNi0.5Mn1.5O4 (LMNO) as cathode material at increased cut-off potentials (>4.5 V vs. Li/Li+). A strong dependence of the formation of organophosphates on the applied electrode potential was observed and investigated by quantitative analysis of the formed phosphates. In addition, new possible ;fingerprint; compounds for describing the electrolyte status were investigated and compared to existing compounds.

Plasma synthesis of lithium based intercalation powders for solid polymer electrolyte batteries

DOEpatents

Kong, Peter C [Idaho Falls, ID; Pink, Robert J [Pocatello, ID; Nelson, Lee O [Idaho Falls, ID

2005-01-04

The invention relates to a process for preparing lithium intercalation compounds by plasma reaction comprising the steps of: forming a feed solution by mixing lithium nitrate or lithium hydroxide or lithium oxide and the required metal nitrate or metal hydroxide or metal oxide and between 10-50% alcohol by weight; mixing the feed solution with O.sub.2 gas wherein the O.sub.2 gas atomizes the feed solution into fine reactant droplets, inserting the atomized feed solution into a plasma reactor to form an intercalation powder; and if desired, heating the resulting powder to from a very pure single phase product.

Methods for achieving the equilibrium number of phases in mixtures suitable for use in battery electrodes, e.g., for lithiating FeS.sub.2

DOEpatents

Guidotti, Ronald A.

1988-01-01

In a method for preparing lithiated, particulate FeS.sub.2 useful as a catholyte material in a lithium thermal battery, whereby the latter's voltage regulation properties are improved, comprising admixing FeS.sub.2 and an amount of a lithium-containing compound whereby the resultant total composition falls in an invariant region of the metallurgical phase diagram of its constituent components, an improvement comprises admixing said lithium-containing compound and FeS.sub.2 together with a solid electrolyte compatible with said catholyte, and heating the mixture at a temperature above the melting point of said electrolyte and at which said mixture reaches its thermodynamic equilibrium number of phases.

Phase Equilibria of Stored Chemical Energy Reactants.

DTIC Science & Technology

1984-07-25

aluminate-lithium ferrate system. Detection of a Li1 Al4/7Fe 3/704 compound: C. R. Acad. Sci., Ser. C, V. 273, No. 15, p. 888-90. McNicol, B. D. and Pott...thermodynamic properties of lithium ferrate (LiO.5Fe2 .504) and lithium aluminate (LiO 5Al 2 504) from 5 to 545 K: J. Chem. Thermodyn., V. 7, No. 7, p. 693- 2...1977, Study of low-temperature hydrothermal crystallization in lithium oxide-silicon dioxide-water, potassium oxide-silicon dioxide-water, and

Solid solution lithium alloy cermet anodes

DOEpatents

Richardson, Thomas J.

2013-07-09

A metal-ceramic composite ("cermet") has been produced by a chemical reaction between a lithium compound and another metal. The cermet has advantageous physical properties, high surface area relative to lithium metal or its alloys, and is easily formed into a desired shape. An example is the formation of a lithium-magnesium nitride cermet by reaction of lithium nitride with magnesium. The reaction results in magnesium nitride grains coated with a layer of lithium. The nitride is inert when used in a battery. It supports the metal in a high surface area form, while stabilizing the electrode with respect to dendrite formation. By using an excess of magnesium metal in the reaction process, a cermet of magnesium nitride is produced, coated with a lithium-magnesium alloy of any desired composition. This alloy inhibits dendrite formation by causing lithium deposited on its surface to diffuse under a chemical potential into the bulk of the alloy.

Method of preparing electrolyte for use in fuel cells

DOEpatents

Kinoshita, Kimio; Ackerman, John P.

1978-01-01

An electrolyte compact for fuel cells includes a particulate support material of lithium aluminate that contains a mixture of alkali metal compounds, such as carbonates or hydroxides, as the active electrolyte material. The porous lithium aluminate support structure is formed by mixing alumina particles with a solution of lithium hydroxide and another alkali metal hydroxide, evaporating the solvent from the solution and heating to a temperature sufficient to react the lithium hydroxide with alumina to form lithium aluminate. Carbonates are formed by reacting the alkali metal hydroxides with carbon dioxide gas in an exothermic reaction which may proceed simultaneously with the formation with the lithium aluminate. The mixture of lithium aluminate and alkali metal in an electrolyte active material is pressed or otherwise processed to form the electrolyte structure for assembly into a fuel cell.

Electrolytic Deposition and Diffusion of Lithium onto Magnesium-9 Wt Pct Yttrium Bulk Alloy in Low-Temperature Molten Salt of Lithium Chloride and Potassium Chloride

NASA Astrophysics Data System (ADS)

Dong, Hanwu; Wu, Yaoming; Wang, Lidong; Wang, Limin

2009-10-01

The electrolytic deposition and diffusion of lithium onto bulk magnesium-9 wt pct yttrium alloy cathode in molten salt of 47 wt pct lithium chloride and 53 wt pct potassium chloride at 693 K were investigated. Results show that magnesium-yttrium-lithium ternary alloys are formed on the surface of the cathodes, and a penetration depth of 642 μm is acquired after 2 hours of electrolysis at the cathodic current density of 0.06 A·cm-2. The diffusion of lithium results in a great amount of precipitates in the lithium containing layer. These precipitates are the compound of Mg41Y5, which arrange along the grain boundaries and hinder the diffusion of lithium, and solid solution of yttrium in magnesium. The grain boundaries and the twins of the magnesium-9 wt pct yttrium substrate also have negative effects on the diffusion of lithium.

PERFLUORINATED AROMATIC COMPOUND

DTIC Science & Technology

octafluorobiphenyl, and perfluoroaliphatic aldehydes. Synthetic routes to perfluoro cyclohexyls via reactions of phenyl and pentafluorphenyl lithium with...other perfluorinated aromatic compounds were employed in the synthesis of perfluorinated aromatic model compounds and polymers. The hydrogenic analogues...hydrazides, and imides. Synthetic routes to perfluoro aralkyl compounds are being investigated. Starting materials are tetrafluorobenzene

Electrochemical cell and method of assembly

DOEpatents

Shimotake, Hiroshi; Voss, Ernst C. H.; Bartholme, Louis G.

1979-01-01

A method of preparing an electrochemical cell is disclosed which permits the assembly to be accomplished in air. The cell includes a metal sulfide as the positive electrode reactant, lithium alloy as the negative electrode reactant and an alkali metal, molten salt electrolyte. Positive electrode reactant is introduced as Li.sub.2 FeS.sub.2, a single-phase compound produced by the reaction of Li.sub.2 S and FeS. The use of this compound permits introduction of lithium in an oxidized form. Additional lithium can be introduced in the negative electrode structure enclosed within an aluminum foil envelope between layers of porous aluminum. Molten salt electrolyte is added after assembly and evacuation of the cell by including an interelectrode separator that has been prewet with an organic solution of KCl.

Improved methods for achieving the equilibrium number of phases in mixtures suitable for use in battery electrodes e. g. , for lithiating FeS/sub 2/

DOEpatents

Guidotti, R.A.

1986-06-10

A method is disclosed for preparing lithiated, particulate FeS/sub 2/ useful as a catholyte material in a lithium thermal battery, whereby the latter's voltage regulation properties are improved. The method comprises admixing FeS/sub 2/ and an amount of a lithium-containing compound, whereby the resultant total composition falls in an invariant region of the metallurgical phase diagram of its constituent components. Said lithium-containing compound and FeS/sub 2/ are admixed together with a solid electrolyte compatible with said catholyte, and the mixture is heated at a temperature above the melting point of said electrolyte and at which said mixture reaches its thermodynamic equilibrium number of phases.

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

DOE PAGES

Hong, Liang; Li, Linsen; Chen-Wiegart, Yuchen-Karen; ...

2017-10-30

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

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

Hong, Liang; Li, Linsen; Chen-Wiegart, Yuchen-Karen

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

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

Hong, Liang; Chen-Wiegart, Yu-Chen K.

2017-10-30

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Chemical overcharge protection of lithium and lithium-ion secondary batteries

DOEpatents

Abraham, Kuzhikalail M.; Rohan, James F.; Foo, Conrad C.; Pasquariello, David M.

1999-01-01

This invention features the use of redox reagents, dissolved in non-aqueous electrolytes, to provide overcharge protection for cells having lithium metal or lithium-ion negative electrodes (anodes). In particular, the invention features the use of a class of compounds consisting of thianthrene and its derivatives as redox shuttle reagents to provide overcharge protection. Specific examples of this invention are thianthrene and 2,7-diacetyl thianthrene. One example of a rechargeable battery in which 2,7-diacetyl thianthrene is used has carbon negative electrode (anode) and spinet LiMn.sub.2 O.sub.4 positive electrode (cathode).

Chemical overcharge protection of lithium and lithium-ion secondary batteries

DOEpatents

Abraham, K.M.; Rohan, J.F.; Foo, C.C.; Pasquariello, D.M.

1999-01-12

This invention features the use of redox reagents, dissolved in non-aqueous electrolytes, to provide overcharge protection for cells having lithium metal or lithium-ion negative electrodes (anodes). In particular, the invention features the use of a class of compounds consisting of thianthrene and its derivatives as redox shuttle reagents to provide overcharge protection. Specific examples of this invention are thianthrene and 2,7-diacetyl thianthrene. One example of a rechargeable battery in which 2,7-diacetyl thianthrene is used has carbon negative electrode (anode) and spinet LiMn{sub 2}O{sub 4} positive electrode (cathode). 8 figs.

Micro-sized organometallic compound of ferrocene as high-performance anode material for advanced lithium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Zhen; Feng, Li; Su, Xiaoru; Qin, Chenyang; Zhao, Kun; Hu, Fang; Zhou, Mingjiong; Xia, Yongyao

2018-01-01

An organometallic compound of ferrocene is first investigated as a promising anode for lithium-ion batteries. The electrochemical properties of ferrocene are conducted by galvanostatic charge and discharge. The ferrocene anode exhibits a high reversible capacity and great cycling stability, as well as superior rate capability. The electrochemical reaction of ferrocene is semi-reversible and some metallic Fe remains in the electrode even after delithiation. The metallic Fe formed in electrode and the stable solid electrolyte interphase should be responsible for its excellent electrochemical performance.

Mineral resource of the month: lithium

USGS Publications Warehouse

Ober, Joyce A.

2006-01-01

Lithium, the lightest metallic element, is silvery, white and soft, and highly reactive. It is used most frequently in chemical compounds or traded as mineral concentrates. Its thermal properties make it an ideal component in thermal shock-resistant ceramics, and its electrochemical properties make it an ideal material for several types of batteries.

The use of lithium to prevent or mitigate alkali-silica reaction in concrete pavements and structures.

DOT National Transportation Integrated Search

2007-03-01

Alkali-silica reaction (ASR) was first identified as a form of concrete deterioration in the late 1930s : (Stanton 1940). Approximately 10 years later, it was discovered that lithium compounds can be used to : control expansion due to ASR. There has ...

Lithium batteries. (Latest citations from the COMPENDEX database). Published Search

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

Not Available

1993-05-01

The bibliography contains citations concerning the design, development, and applications of lithium batteries. Topics include electrochemical aspects, cycling characteristics, performance evaluations, and applications in cardiac pacemaker devices. Batteries using organic compounds, chlorides, and metal sulfides are discussed. (Contains 250 citations and includes a subject term index and title list.)

Intercalation compounds and electrodes for batteries

DOEpatents

Chiang, Yet-Ming; Sadoway, Donald R.; Jang, Young-Il; Huang, Biyan

2004-09-07

This invention concerns intercalation compounds and in particular lithium intercalation compounds which have improved properties for use in batteries. Compositions of the invention include particulate metal oxide material having particles of multicomponent metal oxide, each including an oxide core of at least first and second metals in a first ratio, and each including a surface coating of metal oxide or hydroxide that does not include the first and second metals in the first ratio formed by segregation of at least one of the first and second metals from the core. The core may preferably comprise Li.sub.x M.sub.y N.sub.z O.sub.2 wherein M and N are metal atom or main group elements, x, y and z are numbers from about 0 to about 1 and y and z are such that a formal charge on M.sub.y N.sub.z portion of the compound is (4-x), and having a charging voltage of at least about 2.5V. The invention may also be characterized as a multicomponent oxide microstructure usable as a lithium intercalation material including a multiphase oxide core and a surface layer of one material, which is a component of the multiphase oxide core, that protects the underlying intercalation material from chemical dissolution or reaction. In a particular preferred example the multicomponent oxide may be an aluminum-doped lithium manganese oxide composition. Such aluminum-doped lithium manganese oxide compositions, having an orthorhombic structure, also form a part of the invention. In addition, the invention includes articles, particularly electrodes, for batteries formed from the compositions of the invention, and batteries including such electrodes. The invention further relates to a composite intercalation material comprising at least two compounds in which at least one compound has an orthorhombic structure Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2, where y is nonzero, or a mixture of orthorhombic and monoclinic Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2.

Thigh burns from exploding e-cigarette lithium ion batteries: First case series.

PubMed

Nicoll, K J; Rose, A M; Khan, M A A; Quaba, O; Lowrie, A G

2016-06-01

E-cigarette (EC) use has risen meteorically over the last decade. The majority of these devices are powered by re-chargeable lithium ion batteries, which can represent a fire hazard if damaged, over-heated, over-charged or stored inappropriately. There are currently no reports in the medical literature of lithium ion battery burns related to EC use and no guidance on the appropriate management of lithium ion battery associated injuries. We report two individual cases of burn resulting from explosion of EC re-chargeable lithium ion batteries. Both patients required in-patient surgical management. We provide evidence that lithium ion battery explosions can be associated with mixed thermal and alkali chemical burns, resulting from the significant discharge of thermal energy and the dispersal of corrosive lithium ion compounds. We would recommend, as with other elemental metal exposures, caution in exposing lithium ion battery burns to water irrigation. Early and thorough cleaning and debridement of such burns, to remove residual lithium contamination, may limit the risk of burn wound extension and potentially improve outcomes. Copyright © 2016 Elsevier Ltd and ISBI. All rights reserved.

Lipon coatings for high voltage and high temperature Li-ion battery cathodes

DOEpatents

Dudney, Nancy J.; Liang, Chengdu; Nanda, Jagjit; Veith, Gabriel M.; Kim, Yoongu; Martha, Surendra Kumar

2017-02-14

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

Lipon coatings for high voltage and high temperature Li-ion battery cathodes

DOEpatents

Dudney, Nancy J.; Liang, Chengdu; Nanda, Jagjit; Veith, Gabriel M.; Kim, Yoongu; Martha, Surendra Kumar

2017-12-05

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

Lithium batteries. (Latest citations from the EI Compendex*plus database). Published Search

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

Not Available

1994-12-01

The bibliography contains citations concerning the design, development, and applications of lithium batteries. Topics include electrochemical aspects, cycling characteristics, performance evaluations, and applications in cardiac pacemaker devices. Batteries using organic compounds, chlorides, and metal sulfides are discussed. (Contains 250 citations and includes a subject term index and title list.)

Lithium batteries. (Latest citations from the EI Compendex*plus database). Published Search

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

Not Available

1994-03-01

The bibliography contains citations concerning the design, development, and applications of lithium batteries. Topics include electrochemical aspects, cycling characteristics, performance evaluations, and applications in cardiac pacemaker devices. Batteries using organic compounds, chlorides, and metal sulfides are discussed. (Contains 250 citations and includes a subject term index and title list.)

Li15Al3Si6 (Li14.6Al3.4Si6), a compound displaying a heterographite-like anionic framework.

PubMed

Spina, Laurent; Tillard, Monique; Belin, Claude

2003-02-01

The title compound, lithium aluminium silicide (15/3/6), crystallizes in the hexagonal centrosymmetric space group P6(3)/m. The three-dimensional structure of this ternary compound may be depicted as two interpenetrating lattices, namely a graphite-like Li(3)Al(3)Si(6) layer and a distorted diamond-like lithium lattice. As is commonly found for LiAl alloys, the Li and Al atoms are found to share some crystallographic sites. The diamond-like lattice is built up of Li cations, and the graphite-like anionic layer is composed of Si, Al and Li atoms in which Si and Al are covalently bonded [Si-Al = 2.4672 (4) A].

Safe and recyclable lithium-ion capacitors using sacrificial organic lithium salt.

PubMed

Jeżowski, P; Crosnier, O; Deunf, E; Poizot, P; Béguin, F; Brousse, T

2018-02-01

Lithium-ion capacitors (LICs) shrewdly combine a lithium-ion battery negative electrode capable of reversibly intercalating lithium cations, namely graphite, together with an electrical double-layer positive electrode, namely activated carbon. However, the beauty of this concept is marred by the lack of a lithium-cation source in the device, thus requiring a specific preliminary charging step. The strategies devised thus far in an attempt to rectify this issue all present drawbacks. Our research uncovers a unique approach based on the use of a lithiated organic material, namely 3,4-dihydroxybenzonitrile dilithium salt. This compound can irreversibly provide lithium cations to the graphite electrode during an initial operando charging step without any negative effects with respect to further operation of the LIC. This method not only restores the low CO 2 footprint of LICs, but also possesses far-reaching potential with respect to designing a wide range of greener hybrid devices based on other chemistries, comprising entirely recyclable components.

Lithium Oxysilicate Compounds Final Report.

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

Apblett, Christopher A.; Coyle, Jaclyn

In this study, the structure and composition of lithium silicate thin films deposited by RF magnetron co-sputtering is investigated. Five compositions ranging from Li2Si2O5 to Li8SiO6 were confirmed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and structure analysis on the evolution of non-bridging oxygens in the thin films was conducted with fourier transform infrared (FTIR) spectroscopy. It was found that non-bridging oxygens (NBOs) increased as the silicate network breaks apart with increasing lithium content which agrees with previous studies on lithium silicates. Thin film impurities were examined with x-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectroscopymore » (TOFSIMS) and traced back to target synthesis. This study utilizes a unique synthesis technique for lithium silicate thin films and can be referred to in future studies on the ionic conductivity of lithium silicates formed on the surface of silicon anodes in lithium ion batteries.« less

Safe and recyclable lithium-ion capacitors using sacrificial organic lithium salt

NASA Astrophysics Data System (ADS)

Jeżowski, P.; Crosnier, O.; Deunf, E.; Poizot, P.; Béguin, F.; Brousse, T.

2018-02-01

Lithium-ion capacitors (LICs) shrewdly combine a lithium-ion battery negative electrode capable of reversibly intercalating lithium cations, namely graphite, together with an electrical double-layer positive electrode, namely activated carbon. However, the beauty of this concept is marred by the lack of a lithium-cation source in the device, thus requiring a specific preliminary charging step. The strategies devised thus far in an attempt to rectify this issue all present drawbacks. Our research uncovers a unique approach based on the use of a lithiated organic material, namely 3,4-dihydroxybenzonitrile dilithium salt. This compound can irreversibly provide lithium cations to the graphite electrode during an initial operando charging step without any negative effects with respect to further operation of the LIC. This method not only restores the low CO2 footprint of LICs, but also possesses far-reaching potential with respect to designing a wide range of greener hybrid devices based on other chemistries, comprising entirely recyclable components.

Oligo(ethylene glycol)-functionalized disiloxanes as electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhengcheng; Dong, Jian; West, Robert; Amine, Khalil

Functionalized disiloxane compounds were synthesized by attaching oligo(ethylene glycol) chains, -(CH 2CH 2O)- n, n = 2-7, via hydrosilation, dehydrocoupling, and nucleophilic substitution reactions and were examined as non-aqueous electrolyte solvents in lithium-ion cells. The compounds were fully characterized by 1H, 13C, and 29Si nuclear magnetic resonance (NMR) spectroscopy. Upon doping with lithium bis(oxalato)borate (LiBOB) or LiPF 6, the disiloxane electrolytes showed conductivities up to 6.2 × 10 -4 S cm -1 at room temperature. The thermal behavior of the electrolytes was studied by differential scanning calorimetry, which revealed very low glass transition temperatures before and after LiBOB doping and much higher thermal stability compared to organic carbonate electrolytes. Cyclic voltammetry measurements showed that disiloxane-based electrolytes with 0.8 M LiBOB salt concentration are stable to 4.7 V. The LiBOB/disiloxane combinations were found to be good electrolytes for lithium-ion cells; unlike LiPF 6, LiBOB can provide a good passivation film on the graphite anode. The LiPF 6/disiloxane electrolyte was enabled in lithium-ion cells by adding 1 wt% vinyl ethylene carbonate (VEC). Full cell performance tests with LiNi 0.80Co 0.15Al 0.05O 2 as the cathode and mesocarbon microbead (MCMB) graphite as the anode show stable cyclability. The results demonstrate that disiloxane-based electrolytes have considerable potential as electrolytes for use in lithium-ion batteries.

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

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

Lithium batteries. (Latest citations from the EI Compendex*plus database). Published Search

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

NONE

1997-02-01

The bibliography contains citations concerning the design, development, and applications of lithium batteries. Topics include electrochemical aspects, cycling characteristics, performance evaluations, and applications in cardiac pacemaker devices. Batteries using organic compounds, chlorides, and metal sulfides are discussed. (Contains 50-250 citations and includes a subject term index and title list.) (Copyright NERAC, Inc. 1995)

Lithium batteries. (Latest citations from the EI Compendex*plus database). Published Search

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

NONE

1995-10-01

The bibliography contains citations concerning the design, development, and applications of lithium batteries. Topics include electrochemical aspects, cycling characteristics, performance evaluations, and applications in cardiac pacemaker devices. Batteries using organic compounds, chlorides, and metal sulfides are discussed. (Contains 50-250 citations and includes a subject term index and title list.) (Copyright NERAC, Inc. 1995)

Doped carbon-sulfur species nanocomposite cathode for Li--S batteries

DOEpatents

Wang, Donghai; Xu, Tianren; Song, Jiangxuan

2015-12-29

We report a heteroatom-doped carbon framework that acts both as conductive network and polysulfide immobilizer for lithium-sulfur cathodes. The doped carbon forms chemical bonding with elemental sulfur and/or sulfur compound. This can significantly inhibit the diffusion of lithium polysulfides in the electrolyte, leading to high capacity retention and high coulombic efficiency.

Rechargeable quasi-solid state lithium battery with organic crystalline cathode

PubMed Central

Hanyu, Yuki; Honma, Itaru

2012-01-01

Utilization of metal-free low-cost high-capacity organic cathodes for lithium batteries has been a long-standing goal, but critical cyclability problems owing to dissolution of active materials into the electrolyte have been an inevitable obstacle. For practical utilisation of numerous cathode-active compounds proposed over the past decades, a novel battery construction strategy is required. We have designed a solid state cell that accommodates organic cathodic reactions in solid phase. The cell was successful at achieving high capacity exceeding 200 mAh/g with excellent cycleability. Further investigations confirmed that our strategy is effective for numerous other redox-active organic compounds. This implies hundreds of compounds dismissed before due to low cycleability would worth a re-visit under solid state design. PMID:22693655

Drug Interactions with Lithium: An Update.

PubMed

Finley, Patrick R

2016-08-01

Lithium has been used for the management of psychiatric illnesses for over 50 years and it continues to be regarded as a first-line agent for the treatment and prevention of bipolar disorder. Lithium possesses a narrow therapeutic index and comparatively minor alterations in plasma concentrations can have significant clinical sequelae. Several drug classes have been implicated in the development of lithium toxicity over the years, including diuretics and non-steroidal anti-inflammatory compounds, but much of the anecdotal and experimental evidence supporting these interactions is dated, and many newer medications and medication classes have been introduced during the intervening years. This review is intended to provide an update on the accumulated evidence documenting potential interactions with lithium, with a focus on pharmacokinetic insights gained within the last two decades. The clinical relevance and ramifications of these interactions are discussed.

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

NASA Technical Reports Server (NTRS)

DeSilva, J .H. S. R.; Udinwe, V.; Sideris, P. J.; Smart, M. C.; Krause, F. C.; Hwang, C.; Smith, K. A.; Greenbaum, S. G.

2012-01-01

Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

A novel small-molecule compound of lithium iodine and 3-hydroxypropionitride as a solid-state electrolyte for lithium–air batteries

DOE PAGES

Liu, Fang -Chao; Shadike, Zulipiya; Wang, Xiao -Fang; ...

2016-06-16

A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I–-anion conductor of LiI(HPN) 2 reported previously. Solid-state lithium–air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g –1 with a cyclic performance over 10 cycles. Lastly, our findings provide a new way to design solid-state electrolytes toward high-performance lithium–air batteries.

Car-Parrinello molecular dynamics study of the charge-discharge cycle in lithium-ion battery materials

NASA Astrophysics Data System (ADS)

Kung, Y. F.; Jia, C. J.; Gent, W. E.; Lee, I.; Moritz, B.; Devereaux, T. P.

Lithium-ion transition metal oxide compounds have shown great potential for use as battery electrodes. However, the underlying structural modifications which accompany delithiation during battery charging remain less well understood. Formation of peroxide-like species and cation migration between layers comprise two promising candidates for describing numerous experimental observations. Taking Li2RuO3 as a model system, we use Car-Parrinello molecular dynamics to examine the structural changes that occur during delithiation and lithiation. We compare our results to existing experimental observations in other compounds and provide guidance for future experiments, including resonant inelastic x-ray scattering (RIXS).

Chemistry, Characterization and Processing of IMC Curing Polymers.

DTIC Science & Technology

1983-07-01

example, nitronium hexafluorosilicate (Ref- erence 110), nitronium hexafluorophosphate (Reference 111) and nitronium trifluorometh- anesulfonate(triflate...CCLtoo) "C The dilithio compound underwent lithium -halogen exchange instead of displacement with bromophenylacetylene (Reference 129) due to the...positive character of the bromine on l-bromo-2-phenylacetylene. The reaction product of the lithium -bromine exchange reaction ൭ was identified as 1,4

Stability and ionic mobility in argyrodite-related lithium-ion solid electrolytes.

PubMed

Chen, Hao Min; Maohua, Chen; Adams, Stefan

2015-07-07

In the search for fast lithium-ion conducting solids for the development of safe rechargeable all-solid-state batteries with high energy density, thiophosphates and related compounds have been demonstrated to be particularly promising both because of their record ionic conductivities and their typically low charge transfer resistances. In this work we explore a wide range of known and predicted thiophosphates with a particular focus on the cubic argyrodite phase with a robust three-dimensional network of ion migration pathways. Structural and hydrolysis stability are calculated employing density functional method in combination with a generally applicable method of predicting the relevant critical reaction. The activation energy for ion migration in these argyrodites is then calculated using the empirical bond valence pathway method developed in our group, while bandgaps of selected argyrodites are calculated as a basis for assessing the electrochemical window. Findings for the lithium compounds are also compared to those of previously known copper argyrodites and hypothetical sodium argyrodites. Therefrom, guidelines for experimental work are derived to yield phases with the optimum balance between chemical stability and ionic conductivity in the search for practical lithium and sodium solid electrolyte materials.

Experimental study on beryllium-7 production via sequential reactions in lithium-containing compounds irradiated by 14 MeV neutrons

NASA Astrophysics Data System (ADS)

Maekawa, F.; Verzilov, Y. M.; Smith, D. L.; Ikeda, Y.

2000-12-01

Except for 3H and 14C, no radioactive nuclide is produced by neutron-induced reactions with lithium in lithium-containing materials such as Li 2O and Li 2CO 3. However, when the lithium-containing materials are irradiated by 14 MeV neutrons, radioactive 7Be is produced by sequential charged particle reactions (SCPR). In this study, we measured effective 7Be production cross-sections in several lithium-containing samples at 14 MeV: the cross-sections are in the order of μb. Estimation of the effective cross-sections is attempted, and the estimated values agreed well with the experimental data. It was shown that the 7Be activity in a unit volume of lithium-containing materials in D-T fusion reactors can exceed total activity of the same unit volume of the SiC structural material in a certain cooling time. Consequently, a careful consideration of the 7Be production by SCPR is required to assess radioactive inventories in lithium-containing D-T fusion blanket materials.

The Electrical Conductivity of Li2SO4: LiBr: 0.07 K2SO4.

DTIC Science & Technology

1978-09-01

1ca , R SUM On a synthétlaë un electrolyte solide ~ base de sulfate de lithium en combinant du bromure de lithium et du sulfate de potassium; il...UNCLASSI?I~~ - —~ —. - ~~~~~~~~~~~~~~~~~~~~~~~~~~ .--._ .. ~~~~~~~~~ .. 2 UN~LASSIPI~) Lithium salts, on the other hand , are not only less costly...but they also yield terminal voltages >2 V in certain electroch.mical cells. On . of the earliest lithium compounds to be invest igated i. LiI which has

Protective coating on positive lithium-metal-oxide electrodes for lithium batteries

DOEpatents

Johnson, Christopher S.; Thackeray, Michael M.; Kahaian, Arthur J.

2006-05-23

A positive electrode for a non-aqueous lithium cell comprising a LiMn_2-xM_xO₄ spinel structure in which M is one or more metal cations with an atomic number less than 52, such that the average oxidation state of the manganese ions is equal to or greater than 3.5, and in which 0.ltoreq.x.ltoreq.0.15, having one or more lithium spine oxide LiM'₂O₄ or lithiated spinel oxide Li_1+yM'₂O₄ compounds on the surface thereof in which M' are cobalt cations and in which 0.ltoreq.y.ltoreq.1.

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

PubMed Central

Evans, M. H.

1969-01-01

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

Enhanced cycling performance of a Li metal anode in a dimethylsulfoxide-based electrolyte using highly concentrated lithium salt for a lithium-oxygen battery

NASA Astrophysics Data System (ADS)

Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

2016-03-01

Stable charge-discharge cycling behavior for a lithium metal anode in a dimethylsulfoxide (DMSO)-based electrolyte is strongly desired of lithium-oxygen batteries, because the Li anode is rapidly exhausted as a result of side reactions during cycling in the DMSO solution. Herein, we report a novel electrolyte design for enhancing the cycling performance of Li anodes by using a highly concentrated DMSO-based electrolyte with a specific Li salt. Lithium nitrate (LiNO3), which forms an inorganic compound (Li2O) instead of a soluble product (Li2S) on a lithium surface, exhibits a >20% higher coulombic efficiency than lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate, regardless of the loading current density. Moreover, the stable cycling of Li anodes in DMSO-based electrolytes depends critically on the salt concentration. The highly concentrated electrolyte 4.0 M LiNO3/DMSO displays enhanced and stable cycling performance comparable to that of carbonate-based electrolytes, which had not previously been achieved. We suppose this enhancement is due to the absence of free DMSO solvent in the electrolyte and the promotion of the desolvation of Li ions on the solid electrolyte interphase surface, both being consequences of the unique structure of the electrolyte.

Thermal neutron detector and gamma-ray spectrometer utilizing a single material

DOEpatents

Stowe, Ashley; Burger, Arnold; Lukosi, Eric

2017-05-02

A combined thermal neutron detector and gamma-ray spectrometer system, including: a detection medium including a lithium chalcopyrite crystal operable for detecting thermal neutrons in a semiconductor mode and gamma-rays in a scintillator mode; and a photodetector coupled to the detection medium also operable for detecting the gamma rays. Optionally, the detection medium includes a .sup.6LiInSe.sub.2 crystal. Optionally, the detection medium comprises a compound formed by the process of: melting a Group III element; adding a Group I element to the melted Group III element at a rate that allows the Group I and Group III elements to react thereby providing a single phase I-III compound; and adding a Group VI element to the single phase I-III compound and heating; wherein the Group I element includes lithium.

Choline in the treatment of rapid-cycling bipolar disorder: clinical and neurochemical findings in lithium-treated patients.

PubMed

Stoll, A L; Sachs, G S; Cohen, B M; Lafer, B; Christensen, J D; Renshaw, P F

1996-09-01

This study examined choline augmentation of lithium for rapid-cycling bipolar disorder. Choline bitartrate was given openly to 6 consecutive lithium-treated outpatients with rapid-cycling bipolar disorder. Five patients also underwent brain proton magnetic resonance spectroscopy. Five of 6 rapid-cycling patients had a substantial reduction in manic symptoms, and 4 patients had a marked reduction in all mood symptoms during choline therapy. The patients who responded to choline all exhibited a substantial rise in the basal ganglia concentration of choline-containing compounds. Choline was well tolerated in all cases. Choline, in the presence of lithium, was a safe and effective treatment for 4 of 6 rapid-cycling patients in our series. A hypothesis is suggested to explain both lithium refractoriness in patients with bipolar disorder and the action of choline in mania, which involves the interaction between phosphatidylinositol and phosphatidylcholine second-messenger systems.

Progress in lithium-sulfur batteries: the effective role of a polysulfide-added electrolyte as buffer to prevent cathode dissolution.

PubMed

Lee, Dong-Ju; Agostini, Marco; Park, Ju-Won; Sun, Yang-Kook; Hassoun, Jusef; Scrosati, Bruno

2013-12-01

Paving the road for sulfur: A unique electrolyte composition designed for the development of stable lithium-sulfur batteries with high energy. A battery with a high and stable capacity is prepared by using an electrolyte containing a dissolved catholyte-type compound, that is, Li2 S8 polysulfide. The cell is characterized by a capacity approaching the theoretical value at a working voltage of 2.1 V, which is remarkable compared to conventional lithium ion batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile and rapid method of synthesizing Lithium Titanate for the use in energy storage

NASA Astrophysics Data System (ADS)

Samuel, J. J.; Beh, K. P.; Yam, F. K.

2018-04-01

Batteries are an important facet in today’s world. With smaller devices being produced, the challenge to power it with long lasting batteries continue to be quite the task. Recently, a new compound has proved its usefulness in battery fabrication that is Lithium Titanate (LTO). In this study a facile method of producing LTO via hydrolysis of Lithium Nitride and Titanium n-Butoxide. The method used in this study produced LTO in under 7 hours, much quicker than the standard processing time for LTO. The produced LTO is characterized using Raman Spectroscopy.

Lithium Storage Mechanisms in Purpurin Based Organic Lithium Ion Battery Electrodes

DTIC Science & Technology

2012-12-11

of several non-renewable cathodes like LiCoO2, LiNiO2, Li2MnO4, LiFePO4 etc.7–10. Current Li-ion battery technologies operating on inorganic insertion...comparable to conventional inorganic insertion cathodes such as LiCoO2 or LiFePO4 and also with recently studied other organic compounds such as

Coordination complex pyrolyzation for the synthesis of nanostructured GeO₂ with high lithium storage properties.

PubMed

Li, Xiaona; Liang, Jianwen; Hou, Zhiguo; Zhu, Yongchun; Wang, Yan; Qian, Yitai

2014-11-21

A new (NH4)3H(Ge7O16)(H2O)2.72 precursor-pyrolyzation approach was designed and developed for the facile synthesis of nanostructured GeO2, avoiding the use of any hazardous or expensive germanium compounds. The products show promising anode application in lithium ion batteries with high capacity and excellent cycling stability.

A density functional theory study on the thermodynamic and dynamic properties of anthraquinone analogue cathode materials for rechargeable lithium ion batteries.

PubMed

Yang, Shu-Jing; Qin, Xiao-Ya; He, Rongxing; Shen, Wei; Li, Ming; Zhao, Liu-Bin

2017-05-21

Organic redox compounds have become the emerging electrode materials for rechargeable lithium ion batteries. The high electrochemical performance provides organic electrode materials with great opportunities to be applied in electric energy storage devices. Among the different types of organic materials, conjugated carbonyl compounds are the most promising type at present, because only they can simultaneously achieve, high energy density, high cycling stability, and high power density. In this research, a series of heteroatom substituted anthraquinone (AQ) derivatives were designed theoretically so that the high theoretical capacity of AQ remained. The discharge and charge mechanism as well as the thermodynamic and dynamic properties of AQ and its derivatives were investigated using first-principles density functional theory. Using heteroatom substitution, both the thermodynamic and dynamic properties of AQ as cathode materials could be largely improved. Among these conjugated carboxyl compounds, BDOZD and BDIOZD with a simultaneously high theoretical capacity and high working potential exhibit the largest energy density of about 780 W h kg -1 , which is 41% larger than that of AQ. The PQD with the smallest value of λ gives the largest charge transfer rate constant, which is about four times as large as the prototype molecule, AQ. The most interesting finding is that the lithium ion transfer plays a very important role in influencing both the discharge potential and electrochemical charge transfer rate. The present study illustrates that theoretical calculations provide a highly effective way to discover potential materials for use with rechargeable lithium ion batteries.

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.

Lithium Resources for the 21st Century

NASA Astrophysics Data System (ADS)

Kesler, S.; Gruber, P.; Medina, P.; Keolian, G.; Everson, M. P.; Wallington, T.

2011-12-01

Lithium is an important industrial compound and the principal component of high energy-density batteries. Because it is the lightest solid element, these batteries are widely used in consumer electronics and are expected to be the basis for battery electric vehicles (BEVs), hybrid electric vehicles (HEVs) and plug-in hybrid electric vehicles (PHEVs) for the 21st century. In view of the large incremental demand for lithium that will result from expanded use of various types of EVs, long-term estimates of lithium demand and supply are advisable. For GDP growth rates of 2 to 3% and battery recycling rates of 90 to 100%, total demand for lithium for all markets is expected to be a maximum of 19.6 million tonnes through 2100. This includes 3.2 million tonnes for industrial compounds, 3.6 million tonnes for consumer electronics, and 12.8 million tonnes for EVs. Lithium-bearing mineral deposits that might supply this demand contain an estimated resource of approximately 39 million tonnes, although many of these deposits have not been adequately evaluated. These lithium-bearing mineral deposits are of two main types, non-marine playa-brine deposits and igneous deposits. Playa-brine deposits have the greatest immediate resource potential (estimated at 66% of global resources) and include the Salar de Atacama (Chile), the source of almost half of current world lithium production, as well as Zabuye (China/Tibet) and Hombre Muerto (Argentina). Additional important playa-brine lithium resources include Rincon (Argentina), Qaidam (China), Silver Peak (USA) and Uyuni (Bolivia), which together account for about 35% of the estimated global lithium resource. Information on the size and continuity of brine-bearing aquifers in many of these deposits is limited, and differences in chemical composition of brines from deposit to deposit require different extraction processes and yield different product mixes of lithium, boron, potassium and other elements. Numerous other brines in playas (Great Salt Lake, Searles Lake), geothermal systems (Salton Sea) and oil fields contain lithium, but in low concentrations that add relatively little to estimated global resources. Igneous deposits, which constitute 26% of estimated global resources, consist largely of pegmatites, including past and present producers at Kings Mountain-Bessemer City (USA), Greenbushes (Australia) and Bikita (Zimbabwe), as well as numerous active prospects, especially in Canada and China. Amenability of these deposits to economic extraction is controlled by mineralogy and zoning of lithium, which vary considerably from deposit to deposit. An additional 8% of global lithium resources is estimated to be present in unusual deposits including largely hectorite clays in volcaniclastic rocks at Kings Valley (USA) and jadarite in lacustrine evaporite deposits (Serbia), which present new challenges to both mining and processing. If this highly varied population of deposits can be converted to reserves, lithium supplies for the 21st century EV market are relatively secure.

Method of preparing a positive electrode for an electrochemical cell

DOEpatents

Tomczuk, Zygmunt

1979-01-01

A method of preparing an electrochemical cell including a metal sulfide as the positive electrode reactant and lithium alloy as the negative electrochemical reactant with an alkali metal, molten salt electrolyte is disclosed which permits the assembly to be accomplished in air. The electrode reactants are introduced in the most part as a sulfide of lithium and the positive electrode metal in a single-phase compound. For instance, Li.sub.2 FeS.sub.2 is a single-phase compound that is produced by the reaction of Li.sub.2 S and FeS. This compound is an intermediate in the positive electrode cycle from FeS.sub.2 to Fe and Li.sub.2 S. Its use minimizes volumetric changes from the assembled to the charged and discharged conditions of the electrode and minimizes electrode material interaction with air and moisture during assembly.

Identification of alkylated phosphates by gas chromatography-mass spectrometric investigations with different ionization principles of a thermally aged commercial lithium ion battery electrolyte.

PubMed

Weber, Waldemar; Kraft, Vadim; Grützke, Martin; Wagner, Ralf; Winter, Martin; Nowak, Sascha

2015-05-15

The thermal aging process of a commercial LiPF6 based lithium ion battery electrolyte has been investigated in view of the formation of volatile phosphorus-containing degradation products. Aging products were analyzed by GC-MS. Structure determination of the products was performed by support of chemical ionization MS in positive and negative modes. A fraction of the discovered compounds belongs to the group of fluorophosphates (phosphorofluoridates) which are in suspect of potential toxicity. This is well known for relative derivatives, e.g. diisopropyl fluorophosphate. Another fraction of the identified compounds belongs to the group of trialkyl phosphates. These compounds may provide a positive impact on the thermal and electrochemical performance of Li-based batteries as repeatedly described in the literature. Copyright © 2015 Elsevier B.V. All rights reserved.

Surey of Alternate Stored Chemical Energy Reactions.

DTIC Science & Technology

1985-12-01

Fr., Report No. CEA-N-1293, 36 p. Pilipovich. D.; Rogers, H. H. and Wilson, R. D., 1972, Chlorine trifluoride oxide. II. Photochemical synthesis...some fluorine and chlorine compounds: Zh. Fiz. Khim., V. 43, No. 2, p. 386-9. Rogers, H. H. and Pilipovich, D., 1973, Oxychlorine trifluoride (Patent...chemical energy reactions has been made for purposes of comparison with the lithium- aluminum /water, lithium/sulfur hexafluoride, and other reaction schemes

All-solid state lithium carbon monofluoride batteries

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

Liang, Chengdu; Rangasamy, Ezhiylmurugan

A solid state lithium carbon monofluoride battery includes an anode comprising Li, a solid electrolyte, and a cathode including CF.sub.x and LPS. The cathode can also include a carbon compound. The solid electrolyte can include LPS. The LPS can include .beta.-Li.sub.3PS.sub.4. The cathode LPS can include .beta.-Li.sub.3PS.sub.4. A method of making a battery is also disclosed.

Free-standing and flexible organic cathode based on aromatic carbonyl compound/carbon nanotube composite for lithium and sodium organic batteries.

PubMed

Yuan, Chenpei; Wu, Qiong; Shao, Qi; Li, Qiang; Gao, Bo; Duan, Qian; Wang, Heng-Guo

2018-05-01

Free-standing and flexible organic cathode based on aromatic carbonyl compound/carbon nanotubes (CNTs) has been successfully synthesized by a simple vacuum filtration strategy. The obtained flexible and free-standing film could be directly used as the binder-, additive- and current collector-free cathode for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). Benefitting from the synergistic effect provided by the aromatic carbonyl compound and CNTs, the flexible organic cathode shows excellent lithium and sodium storage properties, including high reversible capacity (∼150 mAh g -1 at 50 mA g -1 for LIBs and 57.8 mAh g -1 at 25 mA g -1 for SIBs), excellent cycling stability (over 500 cycles for LIBs and 300 cycles for SIBs) and good rate capability (48 mAh g -1 even at 2000 mA g -1 for LIBs and 48 mAh g -1 even at 1000 mA g -1 for SIBs). In view of the simple preparation process and excellent performance, the proposed strategy might open new avenues for the design of high-performance flexible organic electrode for the application in energy storage and conversion. Copyright © 2018 Elsevier Inc. All rights reserved.

Encapsulated Vanadium-Based Hybrids in Amorphous N-Doped Carbon Matrix as Anode Materials for Lithium-Ion Batteries.

PubMed

Long, Bei; Balogun, Muhammad-Sadeeq; Luo, Lei; Luo, Yang; Qiu, Weitao; Song, Shuqin; Zhang, Lei; Tong, Yexiang

2017-11-01

Recently, researchers have made significant advancement in employing transition metal compound hybrids as anode material for lithium-ion batteries and developing simple preparation of these hybrids. To this end, this study reports a facile and scalable method for fabricating a vanadium oxide-nitride composite encapsulated in amorphous carbon matrix by simply mixing ammonium metavanadate and melamine as anode materials for lithium-ion batteries. By tuning the annealing temperature of the mixture, different hybrids of vanadium oxide-nitride compounds are synthesized. The electrode material prepared at 700 °C, i.e., VM-700, exhibits excellent cyclic stability retaining 92% of its reversible capacity after 200 cycles at a current density of 0.5 A g -1 and attractive rate performance (220 mAh g -1 ) under the current density of up to 2 A g -1 . The outstanding electrochemical properties can be attributed to the synergistic effect from heterojunction form by the vanadium compound hybrids, the improved ability of the excellent conductive carbon for electron transfer, and restraining the expansion and aggregation of vanadium oxide-nitride in cycling. These interesting findings will provide a reference for the preparation of transition metal oxide and nitride composites as well. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lithium loss in the solid electrolyte interphase: Lithium quantification of aged lithium ion battery graphite electrodes by means of laser ablation inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectroscopy

NASA Astrophysics Data System (ADS)

Schwieters, Timo; Evertz, Marco; Mense, Maximilian; Winter, Martin; Nowak, Sascha

2017-07-01

In this work we present a new method using LA-ICP-MS to quantitatively determine the lithium content in aged graphite electrodes of a lithium ion battery (LIB) by performing total depth profiling. Matrix matched solid external standards are prepared using a solid doping approach to avoid elemental fractionation effects during the measurement. The results are compared and matched to the established ICP-OES technique for bulk quantification after performing a microwave assisted acid digestion. The method is applied to aged graphite electrodes in order to determine the lithium immobilization (= "Li loss") in the solid electrolyte interphase after the first cycle of formation. For this, different samples including a reference sample are created to obtain varying thicknesses of the SEI covering the electrode particles. By applying defined charging voltages, an initial lithiation process is performed to obtain specific graphite intercalation compounds (GICs, with target stoichiometries of LiC30, LiC18, LiC12 and LiC6). Afterwards, the graphite electrode is completely discharged to obtain samples without mobile, thus active lithium in its lattice. Taking the amount of lithium into account which originates from the residues of the LiPF6 (dissolved in the carbon components containing electrolyte), it is possible to subtract the amount of lithium in the SEI.

Symposium on High Power, Ambient Temperature Lithium Batteries, 180th Meeting of the Electrochemical Society, Phoenix, AZ, Oct. 13-17, 1991, Proceedings

NASA Technical Reports Server (NTRS)

Clark, W. D. K. (Editor); Halpert, Gerald (Editor)

1992-01-01

Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.

Influence of Exposure Conditions on the Efficacy of Lithium Nitrate in Mitigating Alkali Silica Reaction

NASA Astrophysics Data System (ADS)

Zapała-Sławeta, Justyna; Owsiak, Zdzisława

2017-10-01

Lithium nitrate is known to have the highest potential to inhibit alkali silica reaction in concrete. It is well soluble in water and does not increase the pH of concrete pore solution. The extent to which the alkali silica reaction is mitigated is affected by the amount of the applied lithium ions, exposure conditions and by the kind of reactive aggregate. It is known that some lithium compounds such as lithium carbonate or lithium fluoride, when used in insufficient amount, may increase expansion due to alkali silica reaction. This effect was not detected in the presence of lithium nitrate. The aim of this study was to determine the effect of lithium nitrate on alkali silica reaction in mortars exposed to different conditions. Expansion studies were conducted in accordance with the accelerated mortar bar test (ASTM C1260) and the standard mortar bar test (ASTM C227). It was observed that the long-term expansion results are different from the values obtained in the accelerated mortar bar test. Lithium nitrate does not reduce ASR-induced expansion when mortars are stored under conditions specified in ASTM C 227. The microstructure of the mortar samples exposed to different conditions was examined and X-ray microanalysis was performed. The microstructure and compositions of the alkali-silica reaction products varied. The amount of alkali silica gel in mortars with lithium nitrate in which the expansion was high was greater than that in the mortar bars tested by accelerated method.

Hydrothermal synthesis and characterization of novel vanadium oxides and their application as cathodes in lithium secondary batteries

NASA Astrophysics Data System (ADS)

Chirayil, Thomas George

Novel layered or tunneled vanadium oxides are sought as a substitute for the expensive Lisb{x}CoOsb2 cathode material in lithium rechargeable batteries. The hydrothermal synthesis approach was taken in search of new vanadium oxides in the presence of a structure directing cation, TMA. A systematic study was done on the hydrothermal synthesis of the Vsb{2}Osb{5}-TMAOH-LiOH system. It was determined from this study that the pH of the reaction mixture was very critical in the formation of many compounds. Acetic acid utilized to adjust the pH of the reaction mixture in the presence of TMA behaved as a buffer and maintained a constant pH during the reaction. Hydrothermal synthesis conducted between pH 10 and 2 resulted in the formation of 7 compounds. At the highest pH, a well known compound Lisb3VOsb4, was formed. Between pH 5.2-9, a layered compound, TMAVsb3Osb7 resulted. The thermal treatment of TMAVsb3Osb7 under oxygen lead to an oxidized phase, TMAVsb3Osb8, which increased its lithium capacity significantly. Between pH 5-6, a cluster compound, TMAsb8lbrack Vsb{22}Osb{54}(CHsb3COO)rbrack{*}4Hsb2O with the acetate ion trapped inside the caged Vsb{22}Osb{54} cluster, and a layered vanadium oxide, Lisb{x}Vsb{2-delta}Osb{4-delta}{*}Hsb2O was obtained. The Lisb{x}Vsb{2-delta}Osb{4-delta}{*}Hsb2O compound was dehydrated to form Lisb{x}Vsb{2-delta}Osb{4-delta} and the lithium was removed electrochemically to form a new type of "VOsb2". Several alkylamines, DMSO and an additional water molecule were intercalated to swell the layers of Lisb{x}Vsb{2-delta}Osb{4-delta}{*}Hsb2O. Lowering the pH between 3.0-3.5, resulted in layered compound, TMAVsb4Osb{10}, with TMA residing between the layers. Layered compounds, TMAVsb8Osb{20} and TMAsb{0.17}Hsp+sb{0.1}Vsb2Osb5, were obtained at very acidic conditions. The hydrothermally grown TMAsb{0.17}Hsp+sb{0.1}Vsb2Osb5 is similar to the xerogel Vsb2Osb5 intercalated with TMA synthesized by the sol-gel process. Several trends were observed as the pH was varied, in this study. The vanadium coordination changed from only tetrahedra at the highest pH in Lisb3VOsb4, to tetrahedra and square pyramids in TMAVsb3Osb7, to only square pyramids in TMAsb8lbrack Vsb{22}Osb{54}(CHsb3COO)rbrack{*}4Hsb2O,\\ Lisb{x}Vsb{2-delta}Osb{4-delta}{*}Hsb2O and TMAVsb4Osb{10}, to octahedra in TMAVsb8Osb{20} and TMAsb{0.17}Hsp+sb{0.1}Vsb2Osb5. The TMA content in the compounds decreased as the pH was decreased. Electrochemical studies indicated that the lithium capacity of the TMA containing layered compounds increased as the content of TMA decreased. Preliminary shadies indicated that the acids used to adjust the pH of the reaction mixture can also influence the type of products obtained by the hydrothermal method. The synthesis and the detailed characterization of these vanadium oxides are thoroughly discussed in this dissertation.

Recovery of Li from alloys of Al- Li and Li- Al using engineered scavenger compounds

DOEpatents

Riley, W. D.; Jong, B. W.; Collins, W. K.; Gerdemann, S. J.

1994-01-01

A method of producing lithium of high purity from lithium aluminum alloys using an engineered scavenger compound, comprising: I) preparing an engineered scavenger compound by: a) mixing and heating compounds of TiO2 and Li2CO3 at a temperature sufficient to dry the compounds and convert Li.sub.2 CO.sub.3 to Li.sub.2 O; and b) mixing and heating the compounds at a temperature sufficient to produce a scavenger Li.sub.2 O.3TiO.sub.2 compound; II) loading the scavenger into one of two electrode baskets in a three electrode cell reactor and placing an Al-Li alloy in a second electrode basket of the three electrode cell reactor; III) heating the cell to a temperature sufficient to enable a mixture of KCl-LiCl contained in a crucible in the cell to reach its melting point and become a molten bath; IV) immersing the baskets in the bath until an electrical connection is made between the baskets to charge the scavenger compound with Li until there is an initial current and voltage followed by a fall off ending current and voltage; and V) making a connection between the basket electrode containing engineered scavenger compound and a steel rod electrode disposed between the basket electrodes and applying a current to cause Li to leave the scavenger compound and become electrodeposited on the steel rod electrode.

High-pressure/high-temperature synthesis and characterization of the first palladium or platinum containing lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt)

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

Heymann, Gunter, E-mail: Gunter.Heymann@uibk.ac.at; Niehaus, Oliver; Krüger, Hannes

The new lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) were obtained via multianvil high-pressure/high-temperature syntheses at 8 GPa and 1150 °C starting from a stoichiometric mixture of lithium nitride, sulfur, and palladium or platinum. Single crystal structure analyses indicated the space group P2{sub 1}/c (no. 14) with the following lattice parameters and refinement results: a=492.9(1), b=1005.9(2), c=614.9(2) pm, β=110.9 (1)°, R1=0.0165, wR2=0.0308 (all data) for Li{sub 2}Pd{sub 3}S{sub 4} and a=498.2(1), b=1005.5(2), c=613.0(2) pm, β=110.8(1)°, R1=0.0215, wR2=0.0450 (all data) for Li{sub 2}Pt{sub 3}S{sub 4}. The crystal structures are built up from two distinct Pd/Pt sites, one of whichmore » is a special position (0,0,0), two sulfur sites, and one lithium site. The atoms Pd2/Pt2 form isolated square planar PdS{sub 4}/PtS{sub 4} units, whereas the Pd1/Pt1 atoms form pairs of square planar PdS{sub 4}/PtS{sub 4} units, which are connected via a common edge. These two structural motives built up a three-dimensional network structure by linking through common corners. The lithium atoms are positioned inside of the so formed channels. Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) are isostructural to the minerals jaguéite, Cu{sub 2}Pd{sub 3}Se{sub 4} and chrisstanleyite, Ag{sub 2}Pd{sub 3}Se{sub 4}, which are up to now the only representatives of this structure type. Both compounds were studied with respect to their magnetic properties and can be classified as Pauli paramagnetic or diamagnetic. Regarding the possibility of lithium mobility inside the channels, of the structure, solid state {sup 7}Li NMR and high-temperature single crystal investigations revealed localization of the lithium atoms on their crystallographic sites. - Graphical abstract: The ternary lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) were prepared via multianvil high-pressure/high-temperature syntheses. They are built up from square planar PtS{sub 4}/PdS{sub 4} units with lithium located in the channels of the crystal structure. - Highlights: • Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) are the missing sulfide analogue compounds to Cu{sub 2}Pd{sub 3}Se{sub 4} and Ag{sub 2}Pd{sub 3}Se{sub 4}. • The compounds are the first Pd or Pt containing lithium transition-metal sulfides. • Li mobility was investigated via temp. dependent XRD and solid state {sup 7}Li NMR. • Magnetic properties revealed Pauli paramagnetic or diamagnetic contributions.« less

Metal hydride compositions and lithium ion batteries

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

Young, Kwo; Nei, Jean

Heterogeneous metal hydride (MH) compositions comprising a main region comprising a first metal hydride and a secondary region comprising one or more additional components selected from the group consisting of second metal hydrides, metals, metal alloys and further metal compounds are suitable as anode materials for lithium ion cells. The first metal hydride is for example MgH.sub.2. Methods for preparing the composition include coating, mechanical grinding, sintering, heat treatment and quenching techniques.

Li Storage of Calcium Niobates for Lithium Ion Batteries.

PubMed

Yim, Haena; Yu, Seung-Ho; Yoo, So Yeon; Sung, Yung-Eun; Choi, Ji-Won

2015-10-01

New types of niobates negative electrode were studied for using in lithium-ion batteries in order to alternate metallic lithium anodes. The potassium intercalated compound KCa2Nb3O10 and proton intercalated compound HCa2Nb3O10 were studied, and the electrochemical results showed a reversible cyclic voltammetry profile with acceptable discharge capacity. The as-prepared KCa2Nb3O10 negative electrode had a low discharge capacity caused by high overpotential, but the reversible intercalation and deintercalation reaction of lithium ions was activated after exchanging H+ ions for intercalated K+ ions. The initial discharge capacity of HCa2Nb3O10 was 54.2 mAh/g with 92.1% of coulombic efficiency, compared with 10.4 mAh/g with 70.2% of coulombic efficiency for KCa2Nb3O10 at 1 C rate. The improved electrochemical performance of the HCa2Nb3O10 was related to the lower bonding energy between proton cation and perovskite layer, which facilitate Li+ ions intercalating into the cation site, unlike potassium cation and perovskite layer. Also, this negative material can be easily exfoliated to Ca2Nb3O10 layer by using cation exchange process. Then, obtained two-dimensional nanosheets layer, which recently expected to be an advanced electrode material because of its flexibility, chemical stable, and thin film fabricable, can allow Li+ ions to diffuse between the each perovskite layer. Therefore, this new type layered perovskite niobates can be used not only bulk-type lithium ion batteries but also thin film batteries as a negative material.

Binderless composite scintillator for neutron detection

DOEpatents

Hodges, Jason P [Knoxville, TN; Crow, Jr; Lowell, M [Oak Ridge, TN; Cooper, Ronald G [Oak Ridge, TN

2009-03-10

Composite scintillator material consisting of a binderless sintered mixture of a Lithium (Li) compound containing .sup.6Li as the neutron converter and Y.sub.2SiO.sub.5:Ce as the scintillation phosphor, and the use of this material as a method for neutron detection. Other embodiments of the invention include various other Li compounds.

Lithium Dinitramide as an Additive in Lithium Power Cells

NASA Technical Reports Server (NTRS)

Gorkovenko, Alexander A.

2007-01-01

Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.

Unravelling the impact of reaction paths on mechanical degradation of intercalation cathodes for lithium-ion batteries

DOE PAGES

Li, Juchuan; Zhang, Qinglin; Xiao, Xingcheng; ...

2015-10-18

The intercalation compounds are generally considered as ideal electrode materials for lithium-ion batteries thanks to their minimum volume expansion and fast lithium ion diffusion. However, cracking still occurs in those compounds and has been identified as one of the critical issues responsible for their capacity decay and short cycle life, although the diffusion-induced stress and volume expansion are much smaller than those in alloying-type electrodes. Here, we designed a thin-film model system that enables us to tailor the cation ordering in LiNi 0.5Mn 1.5O 4 spinels and correlate the stress patterns, phase evolution, and cycle performances. Surprisingly, we found thatmore » distinct reaction paths cause negligible difference in the overall stress patterns but significantly different cracking behaviors and cycling performances: 95% capacity retention for disordered LiNi 0.5Mn 1.5O 4 and 48% capacity retention for ordered LiNi 0.5Mn 1.5O 4 after 2000 cycles. We were able to pinpoint that the extended solid-solution region with suppressed phase transformation attributed to the superior electrochemical performance of disordered spinel. Furthermore, this work envisions a strategy for rationally designing stable cathodes for lithium-ion batteries through engineering the atomic structure that extends the solid-solution region and suppresses phase transformation.« less

Depth profiling the solid electrolyte interphase on lithium titanate (Li4Ti5O12) using synchrotron-based photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Nordh, Tim; Younesi, Reza; Brandell, Daniel; Edström, Kristina

2015-10-01

The presence of a surface layer on lithium titanate (Li4Ti5O12, LTO) anodes, which has been a topic of debate in scientific literature, is here investigated with tunable high surface sensitive synchrotron-based photoelectron spectroscopy (PES) to obtain a reliable depth profile of the interphase. Li||LTO cells with electrolytes consisting of 1 M lithium hexafluorophosphate dissolved in ethylene carbonate:diethyl carbonate (LiPF6 in EC:DEC) were cycled in two different voltage windows of 1.0-2.0 V and 1.4-2.0 V. LTO electrodes were characterized after 5 and 100 cycles. Also the pristine electrode as such, and an electrode soaked in the electrolyte were analyzed by varying the photon energies enabling depth profiling of the outermost surface layer. The main components of the surface layer were found to be ethers, P-O containing compounds, and lithium fluoride.

Production of intensive negative lithium beam with caesium sputter-type ion source

NASA Astrophysics Data System (ADS)

Lobanov, Nikolai R.

2018-01-01

Compounds of lithium oxide, hydroxide and carbonate, mixed with silver, were prepared for use as a cathode in caesium-sputter ion source. The intention was to determine the procedure which would produce the highest intensity negative lithium beams over extended period and with maximum stability. The chemical composition and properties of the samples were analysed using mass-spectrometry, optical microscopy, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analyses (EDX) and Raman spectroscopy. These analyses showed that the chemical transformations with components resulted from pressing, storage and bake out were qualitatively in agreement with expectations. Intensive negative lithium ion beams >1 μA were delivered using cathodes fabricated from materials with multicomponent chemical composition when the following conditions were met: (i) use of components with moderate enthalpy of formation; (ii) low moisture content at final stage of cathode production and (iii) small concentration of water molecules in hydrate phase in the cathode mixture.

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

DOEpatents

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

Characterization of the Phase Composition of Nanosized Lithium Titanates Synthesized by Inductive Thermal Plasma

NASA Astrophysics Data System (ADS)

Quesnel, François; Soucy, Gervais; Veilleux, Jocelyn; Hovington, Pierre; Zhu, Wen; Zaghib, Karim

The properties of lithium titanates anodes in Li-ion batteries are highly dependent on their secondary constituents. While their main phase is usually constituted of Li4Ti5O12, significant quantity of lithium titanates compounds of various stoichiometry are often present, due to either the processing, usage or aging of the material. These may go underreported, as many of these spectrums overlap or display low signal in X-ray diffraction (XRD). Samples of nanosized lithium titanates synthetized by inductive plasma were characterized by XRD and scanning electron microscopy (SEM), as they provide a regular yet typical crystallite size and shape including multiple phases. A Rietveld refinement was developed to extract the composition of these samples. Mass balance through further annealing and differential scanning calorimetry (DSC) enthalpy measurements from phase transformations were also used as identification and validation techniques.

Ferrocene-Promoted Long-Cycle Lithium-Sulfur Batteries.

PubMed

Mi, Yingying; Liu, Wen; Yang, Ke R; Jiang, Jianbing; Fan, Qi; Weng, Zhe; Zhong, Yiren; Wu, Zishan; Brudvig, Gary W; Batista, Victor S; Zhou, Henghui; Wang, Hailiang

2016-11-14

Confining lithium polysulfide intermediates is one of the most effective ways to alleviate the capacity fade of sulfur-cathode materials in lithium-sulfur (Li-S) batteries. To develop long-cycle Li-S batteries, there is an urgent need for material structures with effective polysulfide binding capability and well-defined surface sites; thereby improving cycling stability and allowing study of molecular-level interactions. This challenge was addressed by introducing an organometallic molecular compound, ferrocene, as a new polysulfide-confining agent. With ferrocene molecules covalently anchored on graphene oxide, sulfur electrode materials with capacity decay as low as 0.014 % per cycle were realized, among the best of cycling stabilities reported to date. With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation-π interactions between Li + of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lithium-containing scintillators for thermal neutron, fast neutron, and gamma detection

DOEpatents

Zaitseva, Natalia P.; Carman, M. Leslie; Faust, Michelle A.

2016-03-01

In one embodiment, a scintillator includes a scintillator material; a primary fluor, and a Li-containing compound, where the Li-containing compound is soluble in the primary fluor, and where the scintillator exhibits an optical response signature for thermal neutrons that is different than an optical response signature for fast neutrons and gamma rays.

Study of Synthesis of N-Nitroborazine Compounds. I. Nitryl Chloride as Nitrating Agent.

DTIC Science & Technology

dinitrogen tetroxide (N2O4) as the solid complexes of boron trifluoride (BF3). Nearly water-white nitryl chloride was obtained in this manner. A tinge of...yellow was attributed to the presence of chlorine . The reaction of nitryl chloride with a model compound, lithium dimethylamide, was found to yield

Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

DOE PAGES

Liu, Haodong; An, Ke; Venkatachalam, Subramanian; ...

2016-04-06

Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Li x/3Ni (3/8-3x/8)Co (1/4-x/4)Mn (3/8+7x/24)O 2 (x = 0.6, HLR) and low Li-rich Li(Li x/3Ni (1/3-x/3)Co (1/3-x/3)Mn(1/3+x/3)O 2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the endmore » of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. The lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate once the high voltage plateau is reached.« less

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-06-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium-sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium-sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium-sulfur cells display discharge capacity of 945 mAh g-1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g-1 at 0.1 C and 730 mAh g-1 at 5 C.

Beneficial synergistic effects of microdose lithium with pyrroloquinoline quinone in an Alzheimer's disease mouse model.

PubMed

Zhao, Lei; Gong, Neng; Liu, Meng; Pan, Xiaoli; Sang, Shaoming; Sun, Xiaojing; Yu, Zhe; Fang, Qi; Zhao, Na; Fei, Guoqiang; Jin, Lirong; Zhong, Chunjiu; Xu, Tianle

2014-12-01

Alzheimer's disease (AD) is a complicated, neurodegenerative disorder involving multifactorial pathogeneses and still lacks effective clinical treatment. Recent studies show that lithium exerts disease-modifying effects against AD. However, the intolerant side effects at conventional effective dosage limit the clinical use of lithium in treating AD. To explore a novel AD treatment strategy with microdose lithium, we designed and synthesized a new chemical, tri-lithium pyrroloquinoline quinone (Li3PQQ), to study the synergistic effects of low-dose lithium and pyrroloquinoline quinone, a native compound with powerful antioxidation and mitochondrial amelioration. The results showed that Li3PQQ at a relative low dose (6 and 12 mg/kg) exhibited more powerful effects in restoring the impairment of learning and memory, facilitating hippocampal long-term potentiation, and reducing cerebral amyloid deposition and phosphorylated tau level in APP/PS1 transgenic mice than that of lithium chloride at both low and high dose (5 and 100 mg/kg). We further found that Li3PQQ inhibited the activity of glycogen synthase kinase-3 and increased the activity of β-amyloid-binding alcohol dehydrogenase, which might underlie the beneficial effects of Li3PQQ on APP/PS1 transgenic mice. Our study demonstrated the efficacy of a novel AD therapeutic strategy targeting at multiple disease-causing mechanisms through the synergistic effects of microdose lithium and pyrroloquinoline quinone. Copyright © 2014 Elsevier Inc. All rights reserved.

Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

PubMed Central

Sun, Xiaoli

2017-01-01

Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te). The adsorption and diffusion of lithium on the stable MX2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in both 2H/1T or 2H/1T' phases. The results show that lithium is energetically favourable for adsorption on MX2 monolayers, which can be semiconductors with a narrow bandgap and metallic materials. Lithium cannot be adsorbed onto 2H-WS2 and 2H-WSe2, which have large bandgaps of 1.66 and 1.96 eV, respectively. The diffusion energy barrier is in the range between 0.17 and 0.64 eV for lithium on MX2 monolayers, while for most of the materials it was found to be around 0.25 eV. Therefore, this work illustrated that most of the MX2 monolayers explored in this work can be used as promising anode materials for lithium ion batteries. PMID:29354342

Rechargeable Thin-film Lithium Batteries

DOE R&D Accomplishments Database

Bates, J. B.; Gruzalski, G. R.; Dudney, N. J.; Luck, C. F.; Yu, Xiaohua

1993-08-01

Rechargeable thin film batteries consisting of lithium metal anodes, an amorphous inorganic electrolyte, and cathodes of lithium intercalation compounds have recently been developed. The batteries, which are typically less than 6 {mu}m thick, can be fabricated to any specified size, large or small, onto a variety of substrates including ceramics, semiconductors, and plastics. The cells that have been investigated include Li TiS{sub 2}, Li V{sub 2}O{sub 5}, and Li Li{sub x}Mn{sub 2}O{sub 4}, with open circuit voltages at full charge of about 2.5, 3.6, and 4.2, respectively. The development of these batteries would not have been possible without the discovery of a new thin film lithium electrolyte, lithium phosphorus oxynitride, that is stable in contact with metallic lithium at these potentials. Deposited by rf magnetron sputtering of Li{sub 3}PO{sub 4} in N{sub 2}, this material has a typical composition of Li{sub 2.9}PO{sub 3.3}N{sub 0.46} and a conductivity at 25{degrees}C of 2 {mu}S/cm. The maximum practical current density obtained from the thin film cells is limited to about 100 {mu}A/cm{sup 2} due to a low diffusivity of Li{sup +} ions in the cathodes. In this work, the authors present a short review of their work on rechargeable thin film lithium batteries.

Correlation of intercalation potential with d-electron configurations for cathode compounds of lithium-ion batteries.

PubMed

Chen, Zhenlian; Zhang, Caixia; Zhang, Zhiyong; Li, Jun

2014-07-14

The d-electron localization is widely recognized as important to transport properties of transition metal compounds, but its role in the energy conversion of intercalation reactions of cathode compounds is still not fully explored. In this work, the correlation of intercalation potential with electron affinity, a key energy term controlling electron intercalation, then with d-electron configuration, is investigated. Firstly, we find that the change of the intercalation potential with respect to the transition metal cations within the same structure class is correlated in an approximately mirror relationship with the electron affinity, based on first-principles calculations on three typical categories of cathode compounds including layered oxides and polyoxyanions Then, by using a new model Hamiltonian based on the crystal-field theory, we reveal that the evolution is governed by the combination of the crystal-field splitting and the on-site d-d exchange interactions. Further, we show that the charge order in solid-solution composites and the compatibility of multi-electron redox steps could be inferred from the energy terms with the d-electron configuration alternations. These findings may be applied to rationally designing new chemistry for the lithium-ion batteries and other metal-ion batteries.

Crystal growth of LiIn 1–xGa xSe 2 crystals

DOE PAGES

Wiggins, Brenden; Bell, Joseph; Woodward, Jonathan; ...

2016-10-22

Lithium containing chalcogenide single crystals have become very promising materials for photonics and radiation detection. Detection applications include nuclear nonproliferation, neutron science, and stellar investigations for the search of life. Synthesis and single crystal growth methods for lithium containing chalcogenide, specifically LiIn 1-xGa xSe 2, single crystals are discussed. This study elucidates the possibility of improving neutron detection by reducing the indium capture contribution; with the incorporation of the lithium-6 isotope, gallium substitution may overcome the neutron detection efficiency limitation of 6LiInSe 2 due to appreciable neutron capture by the indium-115 isotope. As a figure of merit, the ternary parentmore » compounds 6LiInSe 2 and 6LiGaSe 2 were included in this study. Quality crystals can be obtained utilizing the vertical Bridgman method to produce quaternary compounds with tunable optical properties. Here, quaternary crystals of varying quality depending on the gallium concentration, approximately 5 x 5 x 2 mm 3 or larger in volume, were harvested, analyzed and revealed tunable absorption characteristics between 2.8-3.4 eV.« less

Diagnostic examination of thermally abused high-power lithium-ion cells

NASA Astrophysics Data System (ADS)

Abraham, D. P.; Roth, E. P.; Kostecki, R.; McCarthy, K.; MacLaren, S.; Doughty, D. H.

The inherent thermal instability of lithium-ion cells is a significant impediment to their widespread commercialization for hybrid-electric vehicle applications. Cells containing conventional organic electrolyte-based chemistries are prone to thermal runaway at temperatures around 180 °C. We conducted accelerating rate calorimetry measurements on high-power 18650-type lithium-ion cells in an effort to decipher the sequence of events leading to thermal runaway. In addition, electrode and separator samples harvested from a cell that was heated to 150 °C then air-quenched to room temperature were examined by microscopy, spectroscopy, and diffraction techniques. Self-heating of the cell began at 84 °C. The gases generated in the cell included CO 2 and CO, and smaller quantities of H 2, C 2H 4, CH 4, and C 2H 6. The main changes on cell heating to 150 °C were observed on the anode surface, which was covered by a thick layer of surface deposits that included LiF and inorganic and organo-phosphate compounds. The sources of gas generation and the mechanisms leading to the formation of compounds observed on the electrode surfaces are discussed.

Failure analysis of the lithium battery: A study of the header deposit on the cell top and diffusion within the electrode glass seal using nuclear microanalysis and FFTIR spectroscopy

NASA Technical Reports Server (NTRS)

Hassan, Razi A.

1991-01-01

The Solid Rocket Booster Range Safety System (SRBRSS) uses a lithium/poly-carbon monofluoride primary battery as a source of electrical power. After cell fabrication and activation, some battery cells have shown self discharge. One possible source of this cell discharge has been suggested to be the formation and growth of a conducting crystallized chemical compound across the glass bead insulator, electrically shorting the glass bead to the casing. This laboratory has begun an analysis of this compound, the glass seal holding the cathode into place, and the cell electrolyte, using Fast Fourier Transform Infrared (FFTIR) Analysis, Rutherford Backscattering Spectroscopy (RBS), and Nuclear Reaction Microanalysis. Preliminary measurements have confirmed the existence of lithium, nitrogen, fluorine, and oxygen on a reddish-brown deposit covering parts of the glass seal holding the positive electrode in place. Cells using Li metal electrodes, have many advantages over conventional primary batteries. One principal disadvantage of using Li batteries on a commercial basis would be the environmental impact of the fluorocarbon material. Another would be the relatively high expense of (CF)n.

Two-dimensional triangular lattice and its application to lithium-intercalated layered compounds

NASA Astrophysics Data System (ADS)

Decerqueira, R. O.

1982-08-01

Good rechargeable batteries are being searched for use in electric vehicles and in energy storage during off-peak consumption periods and from solar sources. The interest in lithium intercalation compounds has been recently enhanced by the search for such batteries. The process of intercalation of lithium in several transition metal dichalcogenides can provide an emf of several volts. The progress achieved in the last decade in the investigation of these intercalates has been facilitated by the availability of the dichalcogenides as single crystals and by their chemical stability. The transition-metal dichalcogenides and their Li-intercalates are studied, with emphasis on the Li/su xTa/sub yTi/sub l-y/S2 series. The interactions between the Li atoms and the applicability of a lattice gas model to the problem of ordering of these atoms is discussed. A formulation is presented of the cluster-variation aproximation to the lattice gas problem. The single-site and the nearest-neighbor triangle basic clusters are considered as models for Li/sub x TiS2. Also a theory is presented for the effects of a random distribution of different species of host atoms, as in Ta/sub y/Ti/sub l-y/S2.

Generation and detection of metal ions and volatile organic compounds (VOCs) emissions from the pretreatment processes for recycling spent lithium-ion batteries.

PubMed

Li, Jia; Wang, Guangxu; Xu, Zhenming

2016-06-01

The recycling of spent lithium-ion batteries brings benefits to both economic and environmental terms, but it can also lead to contaminants in a workshop environment. This study focused on metals, non-metals and volatile organic compounds generated by the discharging and dismantling pretreatment processes which are prerequisite for recycling spent lithium-ion batteries. After discharging in NaCl solution, metal contents in supernate and concentrated liquor were detected. Among results of condition #2, #3, #4 and #5, supernate and concentrated liquor contain high levels of Na, Al, Fe; middle levels of Co, Li, Cu, Ca, Zn; and low levels of Mn, Sn, Cr, Zn, Ba, K, Mg, V. The Hg, Ag, Cr and V are not detected in any of the analyzed supernate. 10wt% NaCl solution was a better discharging condition for high discharge efficiency, less possible harm to environment. To collect the gas released from dismantled LIB belts, a set of gas collecting system devices was designed independently. Two predominant organic vapour compounds were dimethyl carbonate (4.298mgh(-1)) and tert-amylbenzene (0.749mgh(-1)) from one dismantled battery cell. To make sure the concentrations of dimethyl carbonate under recommended industrial exposure limit (REL) of 100mgL(-1), for a workshop on dismantling capacity of 1000kg spent LIBs, the minimum flow rate of ventilating pump should be 235.16m(3)h(-1). Copyright © 2016 Elsevier Ltd. All rights reserved.

Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries

DOE PAGES

Benitez, Laura; Seminario, Jorge M.

2017-05-17

Understanding the transport properties of the solid electrolyte interface (SEI) is a critical piece in the development of lithium ion batteries (LIB) with better performance. We studied the lithium ion diffusivity in the main components of the SEI found in LIB with silicon anodes and performed classical molecular dynamics (MD) simulations on lithium fluoride (LiF), lithium oxide (Li 2O) and lithium carbonate (Li 2CO 3) in order to provide insights and to calculate the diffusion coefficients of Li-ions at temperatures in the range of 250 K to 400 K, which is within the LIB operating temperature range. We find amore » slight increase in the diffusivity as the temperature increases and since diffusion is noticeable at high temperatures, Li-ion diffusion in the range of 130 to 1800 K was also studied and the diffusion mechanisms involved in each SEI compound were analyzed. We observed that the predominant mechanisms of Li-ion diffusion included vacancy assisted and knock-off diffusion in LiF, direct exchange in Li 2O, and vacancy and knock-off in Li 2CO 3. Moreover, we also evaluated the effect of applied electric fields in the diffusion of Li-ions at room temperature.« less

Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries

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

Benitez, Laura; Seminario, Jorge M.

Understanding the transport properties of the solid electrolyte interface (SEI) is a critical piece in the development of lithium ion batteries (LIB) with better performance. We studied the lithium ion diffusivity in the main components of the SEI found in LIB with silicon anodes and performed classical molecular dynamics (MD) simulations on lithium fluoride (LiF), lithium oxide (Li 2O) and lithium carbonate (Li 2CO 3) in order to provide insights and to calculate the diffusion coefficients of Li-ions at temperatures in the range of 250 K to 400 K, which is within the LIB operating temperature range. We find amore » slight increase in the diffusivity as the temperature increases and since diffusion is noticeable at high temperatures, Li-ion diffusion in the range of 130 to 1800 K was also studied and the diffusion mechanisms involved in each SEI compound were analyzed. We observed that the predominant mechanisms of Li-ion diffusion included vacancy assisted and knock-off diffusion in LiF, direct exchange in Li 2O, and vacancy and knock-off in Li 2CO 3. Moreover, we also evaluated the effect of applied electric fields in the diffusion of Li-ions at room temperature.« less

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.

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.

Dissecting anode swelling in commercial lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Ningxin; Tang, Huaqiong

2012-11-01

An innovative method is applied to investigate anode swelling during electrochemical processes in commercial lithium-ion batteries. Cathode surface is partially covered with a piece of paste to block the transportation of lithium ion from active material during charging/discharging, and the corresponding part on the anode film shows no formation of Li-graphite compounds during different electrochemical processes, which is confirmed by XRD analysis. The increases of anode thickness within and outside lithiated zone are measured, and defined as electrochemical swelling and physical swelling respectively. The microscopic lattice expansion of graphite due to lithiation process correlates to mesoscopic electrochemical swelling synchronically, while physical swelling tends to decrease steadily with time. The relationship among the microscopic stress due to lithium-ion intercalation, the mesoscopic stress resulting in anode swelling, and the macroscopic rippling of pouch cell after a large number of cycle test, is analyzed and correlated in terms of stress evolution across different scales, and suggestions for solving anode swelling are provided.

Ascorbic Acid-Assisted Eco-friendly Synthesis of NiCo2O4 Nanoparticles as an Anode Material for High-Performance Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Karunakaran, Gopalu; Maduraiveeran, Govindhan; Kolesnikov, Evgeny; Balasingam, Suresh Kannan; Viktorovich, Lysov Dmitry; Ilinyh, Igor; Gorshenkov, Mikhail V.; Sasidharan, Manickam; Kuznetsov, Denis; Kundu, Manab

2018-05-01

We have synthesized NiCo2O4 nanoparticles (NCO NPs) using an ascorbic acid-assisted co-precipitation method for the first time. When NCO NPs are used as an anode material for lithium-ion batteries, the cell exhibits superior lithium storage properties, such as high capacity (700 mA h g-1 after 300 cycles at 200 mA g-1), excellent rate capabilities (applied current density range 100-1200 mA g-1), and impressive cycling stability (at 1200 mA g-1 up to 650 cycles). The enhanced electrochemical properties of NCO NPs are due to the nanometer dimensions which not only offers a smooth charge-transport pathway and short diffusion paths of the lithium ions but also adequate spaces for volume expansion during Li storage. Hence, this eco-friendly synthesis approach will provide a new strategy for the synthesis of various nanostructured metal oxide compounds, for energy conversion and storage systems applications.

Deuterium and lithium-6 MAS NMR studies of manganese oxide electrode materials

NASA Astrophysics Data System (ADS)

Paik, Younkee

Electrolytic manganese dioxide (EMD) is used world wide as the cathode materials in both lithium and alkaline primary (non-rechargeable) batteries. We have developed deuterium and lithium MAS NMR techniques to study EMD and related manganese oxides and hydroxides, where diffraction techniques are of limited value due to a highly defective nature of the structures. Deuterons in EMD, manganite, groutite, and deuterium-intercalated pyrolusite and ramsdellite were detected by NMR, for the first time, and their locations and motions in the structures were analyzed by applying variable temperature NMR techniques. Discharge mechanisms of EMD in alkaline (aqueous) electrolytes were studied, in conjunction with step potential electrochemical spectroscopic (SPECS) method, and five distinctive discharge processes were proposed. EMD is usually heat-treated at about 300--400°C to remove water to be used in lithium batteries. Details of the effects of heat-treatment, such as structural and compositional changes as a function of heat-treatment temperature, were studied by a combination of MAS NMR, XRD, and thermogravimetric analysis. Lithium local environments in heat-treated EMD (HEMD) that were discharged in lithium cells, were described in terms of related environments found in model compounds pyrolusite and ramsdellite where specific Li + sites were detected by MAS NMR and the hyperfine shift scale method of Grey et al. Acid-leaching of Li2MnO3 represents an approach for synthesizing new or modified manganese oxide electrode materials for lithium rechargeable batteries. Progressive removal of lithium from specific crystallographic sites, followed by a gradual change of the crystal structure, was monitored by a combination of NMR and XRD techniques.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

NASA Technical Reports Server (NTRS)

Huang, Chen-Kuo (Inventor); Smart, Marshall C. (Inventor); Surampudi, Subbarao (Inventor); Bugga, Ratnakumar V. (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

The Synthesis of 1,1’-Bicobaltocene Salts of Tetracyano-P-Quinodimethanide and the Sturcture of 1,1’-Bicobaltocene (Co (III) Co (III)) (TCNQ)3,

DTIC Science & Technology

1981-06-03

Salts of Bicobaltocenet-The hexafluorophosphate salt of bicobaltocene(III,III) was prepared by the method of Davison and Smart 4 and the orange product...tetrahydrofuran. The lithium salt of TCNO was prepared by adding a boiling solution of lithium iodide in acetonitrile to a boiling solution of TCNQ in...compound 1,1’-bicobaltocene[Co(III)Co(III)[TCNQJ 3 resulted from the reaction of the mixed valence hexafluorophosphate salt with a mixture of [Et3NH

Two-dimensional ultra-thin SiO(x) (0 < x < 2) nanosheets with long-term cycling stability as lithium ion battery anodes.

PubMed

Sun, Lin; Su, Tingting; Xu, Lei; Liu, Meipin; Du, Hong-Bin

2016-03-21

Ultra-thin SiO(x) (0 < x < 2) nanosheets were obtained via a convenient solvothermal route from a Zintl compound CaSi2. After carbon coating, the SiOx@C nanosheet anodes exhibit high capacity, good rate and superior cycling performance for high-capacity lithium ion battery applications. The specific capacity can be maintained as high as 760 mA h g(-1) with almost no capacity decay after 400 cycles at a current density of 0.5 A g(-1).

New iron-based mixed-polyanion cathodes for lithium and sodium rechargeable batteries: combined first principles calculations and experimental study.

PubMed

Kim, Hyungsub; Park, Inchul; Seo, Dong-Hwa; Lee, Seongsu; Kim, Sung-Wook; Kwon, Woo Jun; Park, Young-Uk; Kim, Chul Sung; Jeon, Seokwoo; Kang, Kisuk

2012-06-27

New iron-based mixed-polyanion compounds Li(x)Na(4-x)Fe(3)(PO(4))(2)(P(2)O(7)) (x = 0-3) were synthesized, and their crystal structures were determined. The new compounds contained three-dimensional (3D)sodium/lithium paths supported by P(2)O(7) pillars in the crystal. First principles calculations identified the complex 3D paths with their activation barriers and revealed them as fast ionic conductors. The reversible electrode operation was found in both Li and Na cells with capacities of one-electron reaction per Fe atom, 140 and 129 mAh g(-1), respectively. The redox potential of each phase was ∼3.4 V (vs Li) for the Li-ion cell and ∼3.2 V (vs Na) for the Na-ion cell. The properties of high power, small volume change, and high thermal stability were also recognized, presenting this new compound as a potential competitor to other iron-based electrodes such as Li(2)FeP(2)O(7), Li(2)FePO(4)F, and LiFePO(4).

High sulfur-containing carbon polysulfide polymer as a novel cathode material for lithium-sulfur battery.

PubMed

Zhang, Yiyong; Peng, Yueying; Wang, Yunhui; Li, Jiyang; Li, He; Zeng, Jing; Wang, Jing; Hwang, Bing Joe; Zhao, Jinbao

2017-09-12

The lithium-sulfur battery, which offers a high energy density and is environmental friendly, is a promising next generation of rechargeable energy storage system. However, despite these attractive attributes, the commercialization of lithium-sulfur battery is primarily hindered by the parasitic reactions between the Li metal anode and dissolved polysulfide species from the cathode during the cycling process. Herein, we synthesize the sulfur-rich carbon polysulfide polymer and demonstrate that it is a promising cathode material for high performance lithium-sulfur battery. The electrochemical studies reveal that the carbon polysulfide polymer exhibits superb reversibility and cycle stability. This is due to that the well-designed structure of the carbon polysulfide polymer has several advantages, especially, the strong chemical interaction between sulfur and the carbon framework (C-S bonds) inhibits the shuttle effect and the π electrons of the carbon polysulfide compound enhance the transfer of electrons and Li + . Furthermore, as-prepared carbon polysulfide polymer-graphene hybrid cathode achieves outstanding cycle stability and relatively high capacity. This work highlights the potential promise of the carbon polysulfide polymer as the cathode material for high performance lithium-sulfur battery.

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.

Thin-film Rechargeable Lithium Batteries

DOE R&D Accomplishments Database

Bates, J. B.; Gruzalski, G. R.; Dudney, N. J.; Luck, C. F.; Yu, X.

1993-11-01

Rechargeable thin films batteries with lithium metal anodes, an amorphous inorganic electrolyte, and cathodes of lithium intercalation compounds have been fabricated and characterized. The cathodes include TiS{sub 2}, the {omega} phase of V{sub 2}O{sub 5}, and the cubic spinel Li{sub x}Mn{sub 2}O{sub 4} with open circuit voltages at full charge of about 2.5 V, 3.7 V, and 4.2 V, respectively. The development of these robust cells, which can be cycled thousands of times, was possible because of the stability of the amorphous lithium electrolyte, lithium phosphorus oxynitride. This material has a typical composition of Li{sub 2.9}PO{sub 3.3}N{sub 0.46} and a conductivity at 25 C of 2 {mu}S/cm. Thin film cells have been cycled at 100% depth of discharge using current densities of 2 to 100 {mu}A/cm{sup 2}. The polarization resistance of the cells is due to the slow insertion rate of Li{sup +} ions into the cathode. Chemical diffusion coefficients for Li{sup +} ions in the three types of cathodes have been estimated from the analysis of ac impedance measurements.

Metal Cationization Extractive Electrospray Ionization Mass Spectrometry of Compounds Containing Multiple Oxygens

NASA Astrophysics Data System (ADS)

Swanson, Kenneth D.; Spencer, Sandra E.; Glish, Gary L.

2017-06-01

Extractive electrospray ionization is an ambient ionization technique that allows real-time sampling of liquid samples, including organic aerosols. Similar to electrospray ionization, the composition of the electrospray solvent used in extractive electrospray ionization can easily be altered to form metal cationized molecules during ionization simply by adding a metal salt to the electrospray solvent. An increase in sensitivity is observed for some molecules that are lithium, sodium, or silver cationized compared with the protonated molecule formed in extractive electrospray ionization with an acid additive. Tandem mass spectrometry of metal cationized molecules can also significantly improve the ability to identify a compound. Tandem mass spectrometry of lithium and silver cationized molecules can result in an increase in the number and uniqueness of dissociation pathways relative to [M + H]+. These results highlight the potential for extractive electrospray ionization with metal cationization in analyzing complex aerosol mixtures. [Figure not available: see fulltext.

Prevention of paclitaxel-induced peripheral neuropathy by lithium pretreatment

PubMed Central

Mo, Michelle; Erdelyi, Ildiko; Szigeti-Buck, Klara; Benbow, Jennifer H.; Ehrlich, Barbara E.

2012-01-01

Chemotherapy-induced peripheral neuropathy (CIPN) is a debilitating side effect that occurs in many patients undergoing chemotherapy. It is often irreversible and frequently leads to early termination of treatment. In this study, we have identified two compounds, lithium and ibudilast, that when administered as a single prophylactic injection prior to paclitaxel treatment, prevent the development of CIPN in mice at the sensory-motor and cellular level. The prevention of neuropathy was not observed in paclitaxel-treated mice that were only prophylactically treated with a vehicle injection. The coadministration of lithium with paclitaxel also allows for administration of higher doses of paclitaxel (survival increases by 60%), protects against paclitaxel-induced cardiac abnormalities, and, notably, does not interfere with the antitumor effects of paclitaxel. Moreover, we have determined a mechanism by which CIPN develops and have discovered that lithium and ibudilast inhibit development of peripheral neuropathy by disrupting the interaction between paclitaxel, neuronal calcium sensor 1 (NCS-1), and the inositol 1,4,5-trisphosphate receptor (InsP3R) to prevent treatment-induced decreases in intracellular calcium signaling. This study shows that lithium and ibudilast are candidate therapeutics for the prevention of paclitaxel-induced neuropathy and could enable patients to tolerate more aggressive treatment regimens.—Mo, M., Erdelyi, I., Szigeti-Buck, K., Benbow, J. H., Ehrlich, B. E. Prevention of paclitaxel-induced peripheral neuropathy by lithium pretreatment. PMID:22889832

Conductive lithium storage electrode

DOEpatents

Chiang, Yet-Ming [Framingham, MA; Chung, Sung-Yoon [Seoul, KR; Bloking, Jason T [Cambridge, MA; Andersson, Anna M [Uppsala, SE

2008-03-18

A compound comprising a composition A.sub.x(M'.sub.1-aM''.sub.a).sub.y(XD.sub.4).sub.z, A.sub.x(M'.sub.1-aM''.sub.a).sub.y(DXD.sub.4).sub.z, or A.sub.x(M'.sub.1-aM''.sub.a).sub.y(X.sub.2D.sub.7).sub.z, and have values such that x, plus y(1-a) times a formal valence or valences of M', plus ya times a formal valence or valence of M'', is equal to z times a formal valence of the XD.sub.4, X.sub.2D.sub.7, or DXD.sub.4 group; or a compound comprising a composition (A.sub.1-aM''.sub.a).sub.xM'.sub.y(XD.sub.4).sub.z, (A.sub.1-aM''.sub.a).sub.xM'.sub.y(DXD.sub.4).sub.z(A.sub.1-aM''.sub.a).s- ub.xM'.sub.y(X.sub.2D.sub.7).sub.z and have values such that (1-a).sub.x plus the quantity ax times the formal valence or valences of M'' plus y times the formal valence or valences of M' is equal to z times the formal valence of the XD.sub.4, X.sub.2D.sub.7 or DXD.sub.4 group. In the compound, A is at least one of an alkali metal and hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, molybdenum, and tungsten, M'' any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001

Conductive lithium storage electrode

DOEpatents

Chiang, Yet-Ming [Framingham, MA; Chung, Sung-Yoon [Incheon, KR; Bloking, Jason T [Mountain View, CA; Andersson, Anna M [Vasteras, SE

2012-04-03

A compound comprising a composition A.sub.x(M'.sub.1-aM''.sub.a).sub.y(XD.sub.4).sub.z, A.sub.x(M'.sub.1-aM''.sub.a).sub.y(DXD.sub.4).sub.z, or A.sub.x(M'.sub.1-aM''.sub.a).sub.y(X.sub.2D.sub.7).sub.z, and have values such that x, plus y(1-a) times a formal valence or valences of M', plus ya times a formal valence or valence of M'', is equal to z times a formal valence of the XD.sub.4, X.sub.2D.sub.7, or DXD.sub.4 group; or a compound comprising a composition (A.sub.1-aM''.sub.a).sub.xM'.sub.y(XD.sub.4).sub.z, (A.sub.1-aM''.sub.a).sub.xM'.sub.y(DXD.sub.4).sub.z (A.sub.1-aM''.sub.a).sub.xM'.sub.y(X.sub.2D.sub.7).sub.z and have values such that (1-a).sub.x plus the quantity ax times the formal valence or valences of M'' plus y times the formal valence or valences of M' is equal to z times the formal valence of the XD.sub.4, X.sub.2D.sub.7 or DXD.sub.4 group. In the compound, A is at least one of an alkali metal and hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, molybdenum, and tungsten, M'' any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001

Ternary lithium stannides Li xT 3Sn 7-x ( T=Rh, Ir)

NASA Astrophysics Data System (ADS)

Sreeraj, Puravankara; Kurowski, Daniel; Hoffmann, Rolf-Dieter; Wu, Zhiyun; Pöttgen, Rainer

2005-11-01

The ternary stannides Li xRh 3Sn 7-x ( x=0.45, 0.64, 0.80) and Li xIr 3Sn 7-x ( x=0.62 and 0.66) were synthesized from the elements in sealed tantalum tubes in a water-cooled sample chamber of an induction furnace. The samples were characterized by X-ray diffraction on powders and single crystals. The stannides adopt the cubic Ir 3Ge 7-type structure (space group Im3¯m, Z=4). In this structure type the tin atoms occupy the Wyckoff positions 12 d and 16 f and form two interpenetrating frameworks consisting of cubes and square antiprisms. The rhodium and iridium atoms center the square antiprisms and are arranged in pairs. With increasing lithium substitution the lattice parameter of Ir 3Sn 7 (936.7) decreases via 932.2 pm ( x=0.62) to 931.2 pm ( x=0.66), while the Ir-Ir distance remains almost the same (290 pm). A similar trend is observed for the rhodium compounds. The lithium atoms substitute Sn on both framework sites. However, the 16 f site shows a substantially larger preference for Li occupation. This is in contrast to the isotypic magnesium based compounds.

Expert Assessment of Advanced Power Sources

DTIC Science & Technology

2007-07-01

including [13] LiCo1-yNiyO2 , LiNiO2, LiMnO2, LiMn2O4, LiV2O5 and LiFePO4 . The last compound, lithium iron phosphate [19], is attractive as iron is...cheaper and more environmentally friendly than cobalt, nickel or manganese. Commercial development of a lithium ion battery based on LiFePO4 is...electrochemical performance evaluated. Materials studied include: LiV2O5 and other vanadium oxides, LiCoO2, LiMnO2, LiMn2O4 and LiFePO4 . 3-D

Chronic Lithium Treatment in a Rat Model of Basal Forebrain Cholinergic Depletion: Effects on Memory Impairment and Neurodegeneration.

PubMed

Gelfo, Francesca; Cutuli, Debora; Nobili, Annalisa; De Bartolo, Paola; D'Amelio, Marcello; Petrosini, Laura; Caltagirone, Carlo

2017-01-01

Alzheimer's disease (AD) is an age-related neurodegenerative disorder with multifactorial etiopathogenesis, characterized by progressive loss of memory and other cognitive functions. A fundamental neuropathological feature of AD is the early and severe brain cholinergic neurodegeneration. Lithium is a monovalent cation classically utilized in the treatment of mood disorders, but recent evidence also advances a beneficial potentiality of this compound in neurodegeneration. Interestingly, lithium acts on several processes whose alterations characterize the brain cholinergic impairment at short and long term. On this basis, the aim of the present research was to evaluate the potential beneficial effects of a chronic lithium treatment in preventing the damage that a basal forebrain cholinergic neurodegeneration provokes, by investigating memory functions and neurodegeneration correlates. Adult male rats were lesioned by bilateral injections of the immunotoxin 192 IgG-Saporin into the basal forebrain. Starting 7 days before the surgery, the animals were exposed to a 30-day lithium treatment, consisting of a 0.24% Li2CO3 diet. Memory functions were investigated by the open field test with objects, the sociability and preference for social novelty test, and the Morris water maze. Hippocampal and neocortical choline acetyltransferase (ChAT) levels and caspase-3 activity were determined. Cholinergic depletion significantly impaired spatial and social recognition memory, decreased hippocampal and neocortical ChAT levels and increased caspase-3 activity. The chronic lithium treatment significantly rescued memory performances but did not modulate ChAT availability and caspase-3 activity. The present findings support the lithium protective effects against the cognitive impairment that characterizes the brain cholinergic depletion.

Construction of nanostructures for selective lithium ion conduction using self-assembled molecular arrays in supramolecular solids

NASA Astrophysics Data System (ADS)

Moriya, Makoto

2017-12-01

In the development of innovative molecule-based materials, the identification of the structural features in supramolecular solids and the understanding of the correlation between structure and function are important factors. The author investigated the development of supramolecular solid electrolytes by constructing ion conduction paths using a supramolecular hierarchical structure in molecular crystals because the ion conduction path is an attractive key structure due to its ability to generate solid-state ion diffusivity. The obtained molecular crystals exhibited selective lithium ion diffusion via conduction paths consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and small molecules such as ether or amine compounds. In the present review, the correlation between the crystal structure and ion conductivity of the obtained molecular crystals is addressed based on the systematic structural control of the ionic conduction paths through the modification of the component molecules. The relationship between the crystal structure and ion conductivity of the molecular crystals provides a guideline for the development of solid electrolytes based on supramolecular solids exhibiting rapid and selective lithium ion conduction.

Batteries using molten salt electrolyte

DOEpatents

Guidotti, Ronald A.

2003-04-08

An electrolyte system suitable for a molten salt electrolyte battery is described where the electrolyte system is a molten nitrate compound, an organic compound containing dissolved lithium salts, or a 1-ethyl-3-methlyimidazolium salt with a melting temperature between approximately room temperature and approximately 250.degree. C. With a compatible anode and cathode, the electrolyte system is utilized in a battery as a power source suitable for oil/gas borehole applications and in heat sensors.

Polyborylated reagents for modern organic synthesis

PubMed Central

SHIMIZU, Masaki; HIYAMA, Tamejiro

2008-01-01

Diverse kinds of gem- and vic-diborylated compounds are now readily available thanks to advances in gem-diborylation of lithium carbenoids as well as vic-diborylation of carbon–carbon multiple bonds with diboron compounds. These diborylated reagents lead to invention of polyborylated reagents and many novel and useful synthetic methods for supreme stereocontrol. This review summarizes preparative methods and synthetic reactions of di- and polyborylated reagents with the emphasis on multiple bond formation. PMID:18941288

Closer insight into the reactivity of TMP-dialkyl zincates in directed ortho-zincation of anisole: experimental evidence of amido basicity and structural elucidation of key reaction intermediates.

PubMed

Clegg, William; Conway, Ben; Hevia, Eva; McCall, Matthew D; Russo, Luca; Mulvey, Robert E

2009-02-18

The new dialkyl(aryl) lithium zincates [(THF)(2)Li(C(6)H(4)-OMe)MeZnMe] (4), [(TMEDA)Li(C(6)H(4)-OMe)MeZnMe] (6), [(THF)(3)Li(C(6)H(4)-OMe)(t)BuZn(t)Bu] (7), and [(PMDETA)Li(C(6)H(4)-OMe)(t)BuZn(t)Bu] (8) have been prepared by co-complexation reactions of lithiated anisole with the relevant dialkylzinc compound and the relevant Lewis base. These new heterobimetallic compounds have been characterized in solution using (1)H, (13)C{H}, and (7)Li NMR spectroscopy, and the molecular structures of 6 and 8 have been elucidated by X-ray crystallography. In 6 the distinct metals are connected through the anisole ligand which binds in an ambidentate fashion (through carbon-zinc and oxygen-lithium contacts) and also through one of the methyl groups, to close a [LiOCCZnC] six-membered ring; whereas 8 displays an open structure where anisole connects the two metals (in the same mode as in 6) but with the tert-butyl groups exclusively bonded terminally to zinc. Reactivity studies of zincates 4 and 7 with the amine TMP(H) supply experimental evidence that these heterobimetallic compounds are intermediates in the two-step deprotonation reaction of anisole by TMP-dialkyl zincates and show the relevance of the alkyl groups in the efficiency of TMP-dialkyl zincate bases. In addition, important solvent effects have also been evaluated. When hexane is added to THF solutions of compounds 4 or 7, the homoleptic tetraorganozincate [(THF)(2)Li(2)Zn(C(6)H(4)-OMe)(4)] (5) is obtained as the result of a disproportionation process. This lithium-rich zincate has also been spectroscopically and crystallographically characterized.

Rapid detection of economic adulterants in fresh milk by liquid chromatography-tandem mass spectrometry.

PubMed

Abernethy, Grant; Higgs, Kerianne

2013-05-03

A method to aid in the detection of the economically driven adulteration of fresh milk with a range of small, nitrogen containing compounds, including melamine, ammeline, ammelide, cyanuric acid, allantoin, thiourea, urea, biuret, triuret, semicarbazide, aminotriazine, 3- and 4-aminotriazole, cyanamide, dicyandiamide, guanidine, choline, hydroxyproline, nitrate, and a range of amino acids, has been developed. (15)N2-Urea is used as an internal standard. The adulteration of milk with exogenous urea has previously been difficult to detect because of the variation in the naturally occurring levels of urea in milk. However, by monitoring the contaminants biuret and triuret, which comprise up to 1% of synthetic urea, the adulteration of milk with urea-based fertilizer can be detected. We estimate that to be economically viable, adulteration of the order of 90-4000ppm of the above adulterants would need to be added to fresh milk. For most of the compounds, an arbitrary detection threshold of 2ppm is therefore more than sufficient. For biuret, a lower detection threshold, better than 0.5ppm, is desirable and the sensitivity for biuret and triuret can be improved by the post-column addition of lithium to create lithium adducts under electrospray ionisation. Sample handling involves a two-step solvent precipitation method that is deployed in a 96-well plate format, and the hydrophilic interaction liquid chromatography uses a rapid gradient (1.2min). Three separate injections, to detect the positively charged compounds, the negatively charged compounds and amino acids and finally the lithium adducts, are used. This rapid and qualitative survey method may be deployed as a second tier screening method to quickly reduce sample numbers indicated as irregular by an FTIR based screening system, and to direct analysis to appropriate quantification methods. Copyright © 2013 Elsevier B.V. All rights reserved.

High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory

NASA Astrophysics Data System (ADS)

Xiao, Ruijuan; Li, Hong; Chen, Liquan

2015-09-01

Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the density functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compounds is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calculations. β-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivatives of β-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calculations. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles molecular dynamics (FPMD) simulations.

A multi-electron redox mediator for redox-targeting lithium-sulfur flow batteries

NASA Astrophysics Data System (ADS)

Li, Guochun; Yang, Liuqing; Jiang, Xi; Zhang, Tianran; Lin, Haibin; Yao, Qiaofeng; Lee, Jim Yang

2018-02-01

The lithium-sulfur flow battery (LSFB) is a new addition to the rechargeable lithium flow batteries (LFBs) where sulfur or a sulfur compound is used as the cathode material against the lithium anode. We report here our evaluation of an organic sulfide - dimethyl trisulfide (DMTS), as 1) a catholyte of a LFB and 2) a multi-electron redox mediator for discharging and charging a solid sulfur cathode without any conductive additives. The latter configuration is also known as the redox-targeting lithium-sulfur flow battery (RTLSFB). The LFB provides an initial discharge capacity of 131.5 mAh g-1DMTS (1.66 A h L-1), which decreases to 59 mAh g-1DMTS (0.75 A h L-1) after 40 cycles. The RTLSFB delivers a significantly higher application performance - initial discharge capacity of 1225.3 mAh g-1sulfur (3.83 A h L-1), for which 1030.9 mAh g-1sulfur (3.23 A h L-1) is still available after 40 cycles. The significant increase in the discharge and charge duration of the LFB after sulfur addition indicates that DMTS is better used as a redox mediator in a RTLSFB than as a catholyte in a LFB.

Hydrogen mobility in the lightest reversible metal hydride, LiBeH 3

DOE PAGES

Mamontov, Eugene; Kolesnikov, Alexander I.; Sampath, Sujatha; ...

2017-11-24

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH 2, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH 3). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH 2 and LiBeH 3 using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH 2, lithium-beryllium hydride LiBeH 3 exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic thatmore » it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH 2 and LiBeH 3 over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH 3 so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.« less

Hydrogen mobility in the lightest reversible metal hydride, LiBeH 3

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

Mamontov, Eugene; Kolesnikov, Alexander I.; Sampath, Sujatha

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH 2, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH 3). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH 2 and LiBeH 3 using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH 2, lithium-beryllium hydride LiBeH 3 exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic thatmore » it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH 2 and LiBeH 3 over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH 3 so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.« less

RETRACTED: Crystal growth and spectroscopic characterization of Aloevera amino acid added lithium sulfate monohydrate: A non-linear optical crystal

NASA Astrophysics Data System (ADS)

Manimekalai, R.; Antony Joseph, A.; Ramachandra Raja, C.

2014-03-01

This article has been retracted: please see Elsevier Policy on Article Withdrawal. This article has been retracted at the request of authors. According to the author we have reported Aloevera Amino Acid added Lithium sulphate monohydrate [AALSMH] crystal is a new nonlinear optical crystal. From the recorded high performance liquid chromatography spectrum, by matching the retention times with the known compounds, the amino acids present in our extract are identified as homocystine, isoleucine, serine, leucine and tyrosine. From the thin layer chromatography and colorimetric estimation techniques, presence of isoleucine was identified and it was also confirmed by NMR spectrum. From the above studies, we came to conclude that AALSMH is new nonlinear optical crystal. After further investigation, lattice parameter values of AALSMH are coinciding with lithium sulphate. Therefore we have decided to withdraw our paper. Sorry for the inconvenience and time spent.

(sup 6)Li and (sup 7)MAS NMR and In Situ X-Ray Diffraction Studies of Lithium Manganate Cathode Materials

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

Lee, Young Joo; Wang, Francis; Grey, Clare P.

{sup 6}Li MAS NMR spectra of lithium manganese oxides with differing manganese oxidation states (LiMn{sub 2}O{sub 4}, Li{sub 4}Mn{sub 5}O{sub 12}, Li{sub 2}Mn{sub 4}O{sub 9}, and Li{sub 2}Mn{sub 2}O{sub 4}) are presented. Improved understanding of the lithium NMR spectra of these model compounds is used to interpret the local structure of the Li{sub x}Mn{sub 2}O{sub 4} cathode materials following electrochemical Li{sup +} deintercalation to various charging levels. In situ x-ray diffraction patterns of the same material during charging are also reported for comparison. Evidence for two-phase behavior for x <0.4 (Li{sub x}Mn{sub 2}O{sub 4}) is seen by both NMR andmore » diffraction.« less

Synthesis and characterization of cathode, anode and electrolyte materials for rechargeable lithium batteries

NASA Astrophysics Data System (ADS)

Yang, Shoufeng

Two new classes of cathode materials were studied: iron phosphate/sulfate materials and layered manganese oxides, both of which are low cost and had shown some potential. The first class of materials have poor conductivity and cyclability. I studied a number of methods for increasing the conductivity, and determined that grinding the material with carbon black was as effective as special in-situ coatings. The optimum carbon loading was determined to be between 6 and 15 wt%. Too much carbon reduces the volumetric energy density, whereas too little significantly increased cell polarization (reduced the rate of reaction). The kinetic and thermodynamic stability of LiFePO 4 was also studied and it was determined that over discharge protection will be needed as irreversible Li3PO4 can be formed at low potentials. A novel hydrothermal synthesis method was developed, but the significant level of Fe on the Li site reduces the reaction rate too much. In the case of the layered manganese oxide, cation substitution with Co and Ni is found to be effective in avoiding Jahn-Teller effects and improving electrochemistry. A wide range of tin compounds have been suggested as lithium storage media for advanced anode materials, as tin can store over 4 Li per Sn atom. Lithium hexafluorophosphate, LiPF6, is presently the salt of choice for LiCoO2 batteries, but it is expensive and dissolves some manganese compounds. The lithium bis(oxolato)borate (BOB) salt was recently reported, and I made a study of its use in cells with the LiFePO4 cathode and the tin anode. During its synthesis, it became clear that LiBOB is very reactive with many solvents, and these complexes were characterized to better understand this new material. In LiBOB the lithium is five coordinated, an unstable configuration for the lithium ion so that water and many other solvents rapidly react to make a six coordination. Only in the case of ethylene carbonate was the lithium found to be four coordinated. The LiBOB based electrolyte has a lower ionic conductivity than LiPF6, thus providing a poorer performance, while the capacity retention is improved. Further improvement of conductivity is still needed. Improved LiFePO4 cathode materials have been formed, the behavior of pure tin in the form of foil has been determined and will serve as the base case for future studies of tin based anodes, and the structure and electrochemical behavior of the new LIBOB electrolyte salt has been determined. (Abstract shortened by UMI.)

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

Kumada, Nobuhiro, E-mail: kumada@yamanashi.ac.jp; Nakamura, Ayumi; Miura, Akira

A new lithium copper bismuth oxide, LiCuBiO{sub 4} was prepared by hydrothermal reaction using NaBiO{sub 3}0.1*4H{sub 2}O. The crystal structural model of this compound was refined by using synchrotron X-ray powder diffraction data. This bismuthate has the LiCuSbO{sub 4} related structure with the orthorhombic cell (Space group: Pnma) of a=10.9096(9), b=5.8113(5) and c=5.0073(4) Å, and the final R-factors were R{sub wp}=4.84 and R{sub p}=3.58%. This compound is the first example of a lithium copper bismuthate containing Bi{sup 5+}. An antiferromagnetic ordering of Cu{sup 2+} moment was observed at 6 K. - Graphical abstract: In the crystal structure of LiCuBiO{sub 4}more » all metal atoms are coordinated octahedrally by six O atoms and LiO{sub 6} and CuO{sub 6} octahedra form the one-dimensional chains by edge-sharing along the b-axis. The LiO{sub 6} and CuO{sub 6} chains form the layer by face-sharing in the bc plane. The Bi atoms are placed in that interlayer and BiO{sub 6} octahedra are edge-sharing with LiO{sub 6} and CuO{sub 6} octahedra. - Highlights: • A new lithium copper bismuth oxide, LiCuBiO{sub 4} is prepared by hydrothermal reaction. • The crystal structure of LiCuBiO{sub 4} is closely related with that of LiCuSbO{sub 4}. • This new compound exhibits an antiferromagnetic ordering of Cu{sup 2+} moment at 6 K.« less

Redox shuttles for lithium ion batteries

DOEpatents

Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

2014-11-04

Compounds may have general Formula IVA or IVB. ##STR00001## where, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 are each independently selected from H, F, Cl, Br, CN, NO.sub.2, alkyl, haloalkyl, and alkoxy groups; X and Y are each independently O, S, N, or P; and Z' is a linkage between X and Y. Such compounds may be used as redox shuttles in electrolytes for use in electrochemical cells, batteries and electronic devices.

Porcelain enamel neutron absorbing material

DOEpatents

Iverson, D.C.

1987-11-20

A porcelain enamel composition as a neutron absorbing material can be prepared of a major proportion by weight of a cadmium compound and a minor proportion of compound of boron, lithium and silicon. These compounds in the form of a porcelain enamel coating or layer on several alloys has been found to be particularly effective in enhancing the nuclear safety of equipment for use in the processing and storage of fissile material. The composition of the porcelain enamel coating can be tailored to match the coefficient of thermal expansion of the equipment to be coated and excellent coating adhesion can be achieved. 2 figs.

Porcelain enamel neutron absorbing material

DOEpatents

Iverson, Daniel C.

1990-01-01

A porcelain enamel composition as a neutron absorbing material can be prepared of a major proportion by weight of a cadmium compound and a minor proportion of compounds of boron, lithium and silicon. These compounds in the form of a porcelain enamel coating or layer on several alloys has been found to be particularly effective in enhancing the nuclear safety of equipment for use in the processing and storage of fissile material. The composition of the porcelain enamel coating can be tailored to match the coefficient of thermal expansion of the equipment to be coated and excellent coating adhesion can be achieved.

Porcelain enamel neutron absorbing material

DOEpatents

Iverson, Daniel C.

1990-02-06

A porcelain enamel composition as a neutron absorbing material can be prepared of a major proportion by weight of a cadmium compound and a minor proportion of compounds of boron, lithium and silicon. These compounds in the form of a porcelain enamel coating or layer on several alloys has been found to be particularly effective in enhancing the nuclear safety of equipment for use in the processing and storage of fissile material. The composition of the porcelain enamel coating can be tailored to match the coefficient of thermal expansion of the equipment to be coated and excellent coating adhesion can be achieved.

Layered Compounds and Intercalation Chemistry: An Example of Chemistry and Diffusion in Solids.

ERIC Educational Resources Information Center

Whittingham, M. Stanley; Chianelli, Russell R.

1980-01-01

Considers a few areas of oxide/sulfide and intercalation-type chemistry. Discusses synthesis of the disulfides of the metals of group IVB, VB, and VIB; the intercalation reaction between lithium and titanium disulfide; other intercalates; and sulfide catalysts. (CS)

Aqueous lithium air batteries

DOEpatents

Visco, Steven J.; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Petrov, Alexei; Goncharenko, Nikolay

2017-05-23

Aqueous Li/Air secondary battery cells are configurable to achieve high energy density and prolonged cycle life. The cells include a protected a lithium metal or alloy anode and an aqueous catholyte in a cathode compartment. The aqueous catholyte comprises an evaporative-loss resistant and/or polyprotic active compound or active agent that partakes in the discharge reaction and effectuates cathode capacity for discharge in the acidic region. This leads to improved performance including one or more of increased specific energy, improved stability on open circuit, and prolonged cycle life, as well as various methods, including a method of operating an aqueous Li/Air cell to simultaneously achieve improved energy density and prolonged cycle life.

Self-diffusion of electrolyte species in model battery electrodes using Magic Angle Spinning and Pulsed Field Gradient Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Tambio, Sacris Jeru; Deschamps, Michaël; Sarou-Kanian, Vincent; Etiemble, Aurélien; Douillard, Thierry; Maire, Eric; Lestriez, Bernard

2017-09-01

Lithium-ion batteries are electrochemical storage devices using the electrochemical activity of the lithium ion in relation to intercalation compounds owing to mass transport phenomena through diffusion. Diffusion of the lithium ion in the electrode pores has been poorly understood due to the lack of experimental techniques for measuring its self-diffusion coefficient in porous media. Magic-Angle Spinning, Pulsed Field Gradient, Stimulated-Echo Nuclear Magnetic Resonance (MAS-PFG-STE NMR) was used here for the first time to measure the self-diffusion coefficients of the electrolyte species in the LP30 battery electrolyte (i.e. a 1 M solution of LiPF6 dissolved in 1:1 Ethylene Carbonate - Dimethyl Carbonate) in model composites. These composite electrodes were made of alumina, carbon black and PVdF-HFP. Alumina's magnetic susceptibility is close to the measured magnetic susceptibility of the LP30 electrolyte thereby limiting undesirable internal field gradients. Interestingly, the self-diffusion coefficient of lithium ions decreases with increasing carbon content. FIB-SEM was used to describe the 3D geometry of the samples. The comparison between the reduction of self-diffusion coefficients as measured by PFG-NMR and as geometrically derived from FIB/SEM tortuosity values highlights the contribution of specific interactions at the material/electrolyte interface on the lithium transport properties.

Mesoporous LiFeBO3/C hollow spheres for improved stability lithium-ion battery cathodes

NASA Astrophysics Data System (ADS)

Chen, Zhongxue; Cao, Liufei; Chen, Liang; Zhou, Haihui; Zheng, Chunman; Xie, Kai; Kuang, Yafei

2015-12-01

Polyanionic compounds are regarded as one of the most promising cathode materials for the next generation lithium-ion batteries due to their abundant resource and thermal stability. LiFeBO3 has a relatively higher capacity than olivine LiFePO4, however, moisture sensitivity and low conductivity hinder its further development. Here, we design and synthesize mesoporous LiFeBO3/C (LFB/C) hollow spheres to enhance its structural stability and electric conductivity, two LiFeBO3/C electrodes with different carbon content are prepared and tested. The experimental results show that mesoporous LiFeBO3/C hollow spheres with higher carbon content exhibit superior lithium storage capacity, cycling stability and rate capability. Particularly, the LFB/C electrode with higher carbon content demonstrates good structural stability, which can maintain its original crystal structure and Li storage properties even after three months of air exposure at room temperature. The exceptional structural stability and electrochemical performance may justify their potential use as high-performance cathode materials for advanced lithium-ion batteries. In addition, the synthesis strategy demonstrated herein is simple and versatile for the fabrication of other polyanionic cathode materials with mesoporous hollow spherical structure.

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.

LiBi{sub 3}S{sub 5}—A lithium bismuth sulfide with strong cation disorder

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

Nakhal, Suliman; Wiedemann, Dennis, E-mail: dennis.wiedemann@chem.tu-berlin.de; Stanje, Bernhard

Among chalcogenide semiconductors for thermoelectric applications, alkali-metal bismuth compounds occur in many complex compositions favorable for high performance. Although LiBi{sub 3}S{sub 5} had been announced in 1977, the potential 1D lithium-ion conductor has hitherto eluded selective synthesis and structure determination. In this study, we present a solid-state route to phase-pure LiBi{sub 3}S{sub 5} powder starting from LiBiS{sub 2} and Bi{sub 2}S{sub 3}. Neutron diffractograms and lithium NMR spectra reveal its crystal structure to be a cation-disordered variety of the AgBi{sub 3}S{sub 5} type (synthetic pavonite; monoclinic, C2/m). Topological analyses and lithium NMR relaxometry suggest that correlated lithium-ion diffusion with activationmore » energies up to 0.66(2) eV occurs along the channels in b direction including tetrahedral voids. Because of cation disorder, immobile bismuth(III) ions clog these pathways, making LiBi{sub 3}S{sub 5} a moderate to poor ionic conductor. The synthesis route reported is nonetheless promising for new lithium bismuth sulfides with, possibly ordered, structure types of the pavonite homologous series. - Graphical abstract: Phase-pure LiBi{sub 3}S{sub 5} has been synthesized and shown to crystallize in cation-disordered variety of the AgBi{sub 3}S{sub 5} type (synthetic pavonite, C2/m) using neutron diffractometry. Topological analyses and NMR relaxometry suggest that immobile Bi{sup 3+} ions clog migration channels along b, making the material a poor lithium conductor. Display Omitted - Highlights: • Phase-pure LiBi{sub 3}S{sub 5} has been synthesized using a promising solid-state route. • LiBi{sub 3}S{sub 5} crystallizes in a cation-disordered variant of the AgBi{sub 3}S{sub 5} type. • Topological analyses suggest lithium diffusion in channels along b. • NMR relaxometry finds activation energies of diffusion as high as 0.66(2) eV. • Because of disorder, LiBi{sub 3}S{sub 5} is a moderate to poor lithium-ion conductor.« less

LITHIUM CHLORIDE AS CATALYST FOR THE RING-OPENING POLYMERIZATION OF LACTIDE IN THE PRESENCE OF HYDROXYL-CONTAINING COMPOUNDS. (R826123)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Novel polymers and method of preparing same

NASA Technical Reports Server (NTRS)

Hirshfield, S. M. (Inventor)

1973-01-01

Polymers are prepared with terminal functional groups by reacting a compound selected from the group consisting of lithium p-lithiophenoxide and tetrabutylammonium p-lithiophenoxide as an initiator with material such as butadiene. The resulting functionally terminated new polymers are then capable of reacting with coupling agents to form star polymers.

Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides

DOE PAGES

Abdellahi, Aziz; Urban, Alexander; Dacek, Stephen; ...

2016-07-13

Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO 2) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dV/dx u )is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (~4.5-4.7 V). In this study, we develop a lattice model based on first principles to understand andmore » quantify the voltage slope of cation-disordered LiMO 2. We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of highvoltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disorder is generally smaller for highvoltage transition metals than for low-voltage transition metals due to a more effective screening of Li-M interactions by oxygen electrons. Short-range order in practical disordered compounds is found to further mitigate the voltage slope increase upon disorder. In conclusion, our analysis shows that the additional high-voltage tetrahedral capacity induced by disorder is smaller in Liexcess compounds than in stoichiometric LiMO 2 compounds.« less

Characterization of LiBC by phase-contrast scanning transmission electron microscopy.

PubMed

Krumeich, Frank; Wörle, Michael; Reibisch, Philipp; Nesper, Reinhard

2014-08-01

LiBC was used as a model compound for probing the applicability of phase-contrast (PC) imaging in an aberration-corrected scanning transmission electron microscope (STEM) to visualize lithium distributions. In the LiBC structure, boron and carbon are arranged to hetero graphite layers between which lithium is incorporated. The crystal structure is reflected in the PC-STEM images recorded perpendicular to the layers. The experimental images and their defocus dependence match with multi-slice simulations calculated utilizing the reciprocity principle. The observation that a part of the Li positions is not occupied is likely an effect of the intense electron beam triggering Li displacement. Copyright © 2013 Elsevier Ltd. All rights reserved.

High-pressure x-ray diffraction study on lithium borohydride using a synchrotron radiation

NASA Astrophysics Data System (ADS)

Nakano, S.; Nakayama, A.; Kikegawa, T.

2008-07-01

Lithium borohydride (LiBH4) was compressed up to 10 GPa using a diamond-anvil-cell to investigate its high-pressure structure. In-situ x-ray diffraction profiles indicated a pressure-induced transformation at 1.1 GPa, which was consistent with the previous experimental observation such as Raman scattering spectroscopy. The high-pressure phase was indexed on a tetragonal symmetry of P42/mmc, which was not corresponding some structural models proposed by previous calculation studies. An unknown substance (presumably another Li-B-H compound), which was contained in the starting material, also transformed into its high-pressure phase at 0.6 GPa without any relation to the transformation of LiBH4.

Lithium halide monolayers: Structural, electronic and optical properties by first principles study

NASA Astrophysics Data System (ADS)

Safari, Mandana; Maskaneh, Pegah; Moghadam, Atousa Dashti; Jalilian, Jaafar

2016-09-01

Using first principle study, we investigate the structural, electronic and optical properties of lithium halide monolayers (LiF, LiCl, LiBr). In contrast to graphene and other graphene-like structures that form hexagonal rings in plane, these compounds can form and stabilize in cubic shape interestingly. The type of band structure in these insulators is identified as indirect type and ionic nature of their bonds are illustrated as well. The optical properties demonstrate extremely transparent feature for them as a result of wide band gap in the visible range; also their electron transitions are indicated for achieving a better vision on the absorption mechanism in these kinds of monolayers.

Improved electrochemical property of nanoparticle polyoxovanadate K7NiV13O38 as cathode material for lithium battery

NASA Astrophysics Data System (ADS)

Ni, Erfu; Uematsu, Shinya; Quan, Zhen; Sonoyama, Noriyuki

2013-06-01

Molecular cluster ion compound K7NiV13O38 (KNiV) has been studied as a novel cathode material for lithium ion battery. The nanoparticles are prepared by a simple re-crystallization method adding different volumes of acetone to the water solution containing the dissolved KNiV. The KNiV re-crystallized from water/acetone ratio of 1:5 shows the most uniform particle size distribution and the smallest particles with thickness of 100 nm and width of 150 nm. The nanoparticle KNiV shows significant improvement in initial discharge capacity and capacity retention after 50 cycles compared to the as-prepared micro-sized particles at various current densities. Ex situ XRD patterns demonstrate that the discharge-charge process proceeds with amorphous KNiV, which is independent from the crystal structure. Ex situ FT-IR spectra indicate that [NiV13O38]7- cluster ion is stable and reacts reversibly with lithium ion in the discharge-charge process.

Stabilization of cubic Li7La3Hf2O12 by Al-doping

NASA Astrophysics Data System (ADS)

Baklanova, Yana V.; Tyutyunnik, Alexander P.; Tarakina, Nadezda V.; Fortes, A. Dominic; Maksimova, Lidiya G.; Korona, Daniil V.; Denisova, Tatyana A.

2018-07-01

In this paper we report on the stabilization of cubic Li7La3Hf2O12 by Al3+ doping and present a detailed crystal structure study and lithium ion conductivity measurements of the obtained compound. Polycrystalline Al-doped Li7La3Hf2O12 was prepared by a modified solid state method. The compound consists of micrometer size grains encapsulated by a glassy phase, which helps preventing the volatilization of lithium during annealing. Al-doped Li7La3Hf2O12 crystallizes in the garnet-related structure with a cubic unit cell (sp. gr. Ia 3 bar d (230)). A structural refinement using X-ray and neutron powder diffraction data showed that the Al3+ ions occupy only tetrahedral Li+ sites in the structure. The presence of overextended leading edges of the peaks on the XRD and NPD data is described by the introduction of an additional phase with rhombohedral distortion that occurs through a stretching of the cubic phase along the body diagonal. The activation energy as well as the total conductivity at room temperature are close to values obtained for un-doped cubic Li7La3Zr2O12 and Li7La3Hf2O12 garnets, which make Al-doped Li7La3Hf2O12 a potential candidate for the application as solid electrolyte in solid-state rechargeable lithium-ion batteries.

Technologies for Extracting Valuable Metals and Compounds from Geothermal Fluids

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

Harrison, Stephen

2014-04-30

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

Thermal oxidation behavior of an Al-Li-Cu-Mg-Zr alloy

NASA Astrophysics Data System (ADS)

Ahmad, Maqsood

1987-04-01

The chemical composition of oxide films formed during thermal treatments of an Al-Li-Cu-Mg-Zr alloy has been studied by means of Auger electron spectroscopy and X-ray photoelectron spectroscopy. The oxide layers formed after oxidation of 2.5 minutes to 30 minutes at 530 °C in lab air have been characterized. In the early stages of oxidation the surface is composed of both the lithium rich oxides and magnesium rich oxides. However, after longer oxidation times the oxidation of lithium becomes predominant and the air/oxide interface is completely covered by lithium compounds. Oxidation products formed on the alloy surface have been studied by X-ray diffraction analysis. The following three phases, namely, Li2CO3, α-Li5AlO4, and γ-LiAlO2, were identified. During heat treatment in lab air at 530 °C and at atmospheric pressure the dominating reaction product is Li2CO3. Due to the selective oxidation of lithium a soft surface layer is developed. The width of the soft layer formed during solution heat treatments carried out in lab air and in salt bath environments has been determined by microhardness measurements. The lithium concentration profiles were calculated from a diffusion equation. The depletion of alloying elements from the near surface region during heat treatments has been investigated using energy dispersive X-ray analysis. The oxide morphology was examined using scanning electron microscopy and optical microscopy.

Thermal oxidation behavior of an Al-Li-Cu-Mg-Zr alloy

NASA Astrophysics Data System (ADS)

Ahmad, Maqsood

1987-05-01

The chemical composition of oxide films formed during thermal treatments of an Al-Li-Cu-Mg-Zr alloy has been studied by means of Auger electron spectroscopy and X-ray photoelectron spectroscopy. The oxide layers formed after oxidation of 2.5 minutes to 30 minutes at 530 °C in lab air have been characterized. In the early stages of oxidation the surface is composed of both the lithium rich oxides and magnesium rich oxides. However, after longer oxidation times the oxidation of lithium becomes predominant and the air/oxide interface is completely covered by lithium compounds. Oxidation products formed on the alloy surface have been studied by X-ray diffraction analysis. The following three phases, namely, Li2CO3, α-Li5AlO4, and γ-LiAlO2, were identified. During heat treatment in lab air at 530 °C and at atmospheric pressure the dominating reaction product is Li2CO3. Due to the selective oxidation of lithium a soft surface layer is developed. The width of the soft layer formed during solution heat treatments carried out in lab air and in salt bath environments has been determined by microhardness measurements. The lithium concentration profiles were calculated from a diffusion equation. The depletion of alloying elements from the near surface region during heat treatments has been investigated using energy dispersive X-ray analysis. The oxide morphology was examined using scanning electron microscopy and optical microscopy.

Crack-resistant siloxane molding compounds. [Patent application

DOEpatents

McFarland, J.W.; Swearngin, C.B.

1980-11-03

The crack resistance of phenyl silicone molding resins containing siliceous fillers is improved by incorporating therein about 0.5 to 5.5% by weight of ..beta..-eucryptite, a lithium aluminum silicate having a negative thermal expansion coefficient. These molding resins are particularly suitable for encapsulating electronic devices such as diodes, coils, resistors, and the like.

Sulfur/lithium-insertion compound composite cathodes for Li-S batteries

NASA Astrophysics Data System (ADS)

Su, Yu-Sheng; Manthiram, Arumugam

2014-12-01

A part of carbon additives in sulfur cathodes is replaced by lithium-insertion compounds as they can contribute extra capacity and increase the overall energy density. Accordingly, VO2(B) and TiS2 were incorporated into sulfur cathodes as they can work within the same voltage window as that of sulfur. However, VO2(B) was found to be incompatible with the glyme-based electrolytes that are usually used in Li-S cells, but TiS2 performs well while coupled with sulfur. The S/C/TiS2 composite cathode delivers 252 mAh g-1 more than that of pristine sulfur cathode (1334 mAh g-1 vs. 1082 mAh g-1). The increased capacity is not only due to the contribution by TiS2 itself but also due to a better active-material dispersion and utilization. Serving as active reaction sites during cycling, TiS2 suppresses agglomeration of sulfur and facilitates better ionic/electronic transport within the cathode structure. This composite cathode design provides another direction for Li-S batteries to improve the overall energy density.

Synthesis, structural characterization and high pressure phase transitions of monolithium hydronium sulfate

NASA Astrophysics Data System (ADS)

Banerjee, Debasis; Plonka, Anna M.; Kim, Sun Jin; Xu, Wenqian; Parise, John B.

2013-01-01

A three dimensional lithium hydronium sulfate LiSO4·H3O [1], [space group Pna21a=8.7785(12) Å, b=9.1297(12) Å, c=5.2799(7) Å, V=423.16(10) Å3] was synthesized via solvothermal methods using 1,5-naphthalenedisulfonic acid (1,5-NSA) as the source of sulfate ions. The structure of [1], determined by single crystal X-ray diffraction techniques, consists of corner sharing LiO4 and SO4 tetrahedra, forming an anionic 3-D open framework that is charge balanced by hydronium ions positioned within channels running along [001] and forming strong H-bonding with the framework oxygen atoms. Compound [1] undergoes two reversible phase transitions, involving reorientation of SO42- ions at pressures of approximately 2.5 and 5 GPa at room temperature, as evident from characteristic discontinuous frequency drops in the ν1 mode of the Raman spectra. Additionally, compound [1] forms dense β-lithium sulfate at 300 °C, as evident from temperature dependent powder XRD and combined reversible TGA-DSC experiments.

Nanoscale building blocks in a novel lithium arsenotungsten bronze: Synthesis and characterization

DOE PAGES

Zhao, Pei; Mangir Murshed, M.; Huq, Ashfia; ...

2015-02-19

Here we report on a novel compound Li 3AsW 7O 25 obtained by solid-state reaction and characterized by diffraction and spectroscopic methods. The bronze-type compound crystallizes in the orthorhombic space group Pbca with a=724.38(3) pm, b=1008.15(4) pm, c=4906.16(17) pm and Z=8. The structure is built up by chains of WO 6 octahedra interconnected by AsO 4 tetrahedra and WO 6 octahedra forming a polyhedral arrangement as seen in intergrowth tungsten bronzes. The X-ray single crystal structure refinement allows solving the complex arsenotungstate framework. The powder neutron diffraction data analysis locates the lithium atoms. Thermal analysis showed that Li 3AsW 7Omore » 25 is stable up to its melting at 1135(3) K followed by a decomposition at 1182(5) K. Finally, the Kubelka-Munk treatment of the UV-vis spectrum revealed a wide band gap in the range of 2.84-3.40 eV depending on the presumed electron transition type.« less

Identify OH groups in TiOF{sub 2} and their impact on the lithium intercalation properties

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

Li, Wei; Body, Monique; Legein, Christophe

A detailed investigation on the chemical composition of the cubic form of titanium oxyfluoride-based compound reveals the presence of OH groups substituting the oxide/ fluoride sublattice. The substitution of oxide by hydroxyl groups induces the presence of titanium vacancies (□) which were characterized by {sup 1}H and {sup 19}F solid-state NMR. {sup 1}H NMR shows that OH groups are present as bridging Ti-OH-Ti or terminal OH groups, i.e. sitting close to a titanium vacancy Ti-OH-□. The electrochemical properties vs. Li{sup +}/Li indicates that the presence of OH groups prevents the intercalation of lithium in the upper voltage region (1.2–3 Vmore » vs. Li{sup +}/Li). Indeed, a partial dehydroxylation of the framework enables to improve the reversibility of the lithium insertion/de-insertion processes. Since the presence of OH groups in this type of compounds is usual and depends on the synthesis method employed, this work enables to rationalize the different electrochemical behaviors reported in the literature and further highlights the importance of a good knowledge of the chemical composition with regard to the physico-chemical properties. - Graphical abstract: The substitution of oxide by hydroxyl groups inducing the formation of titanium vacancies (□), i.e., Ti{sub 1−x}□{sub x}O{sub 1-4x}(OH){sub 4x+y}F{sub 2−y}, was characterized by solid-state {sup 1}H and {sup 19}F NMR. - Highlights: • Evidences of the presence of OH groups and titanium vacancies in titanium oxyfluoride. • {sup 1}H NMR showed the presence of Ti-OH-Ti and Ti-OH-□ species. • The presence of OH groups limits the insertion of lithium within the interstitial sites.« less

Synthesis, structural characterization and high pressure phase transitions of monolithium hydronium sulfate

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

Banerjee, Debasis, E-mail: debasis.banerjee@stonybrook.edu; Plonka, Anna M.; Kim, Sun Jin

2013-01-15

A three dimensional lithium hydronium sulfate LiSO{sub 4}{center_dot}H{sub 3}O [1], [space group Pna2{sub 1}a=8.7785(12) A, b=9.1297(12) A, c=5.2799(7) A, V=423.16(10) A{sup 3}] was synthesized via solvothermal methods using 1,5-naphthalenedisulfonic acid (1,5-NSA) as the source of sulfate ions. The structure of [1], determined by single crystal X-ray diffraction techniques, consists of corner sharing LiO{sub 4} and SO{sub 4} tetrahedra, forming an anionic 3-D open framework that is charge balanced by hydronium ions positioned within channels running along [001] and forming strong H-bonding with the framework oxygen atoms. Compound [1] undergoes two reversible phase transitions, involving reorientation of SO{sub 4}{sup 2-} ionsmore » at pressures of approximately 2.5 and 5 GPa at room temperature, as evident from characteristic discontinuous frequency drops in the {nu}{sub 1} mode of the Raman spectra. Additionally, compound [1] forms dense {beta}-lithium sulfate at 300 Degree-Sign C, as evident from temperature dependent powder XRD and combined reversible TGA-DSC experiments. - Graphical abstract: Left: View of corner-shared LiO{sub 4} and SO{sub 4} tetrahedra along [001] direction with hydronium ions situated in the channels. Right: (a) Photograph of the loaded DAC (b) Ambient pressure Raman spectrum of compound [1] (c) Evolution of the {nu}{sub 1} mode with the increasing and decreasing pressure indicating transitions to high-pressure phases at {approx}2.5 (red curves) and {approx}5 GPa (blue curves) and at {approx}3.5 GPa upon decompression. Highlights: Black-Right-Pointing-Pointer A 3-D lithium hydronium sulfate is synthesized by solvothermal methods. Black-Right-Pointing-Pointer Two high pressure phase transition occurs due to rotation of sulfate groups. Black-Right-Pointing-Pointer The framework undergoes a high temperature structural transformation, to form {beta}-Li{sub 2}SO{sub 4} phase.« less

Investigation of the Storage Behavior of Shredded Lithium-Ion Batteries from Electric Vehicles for Recycling Purposes.

PubMed

Grützke, Martin; Krüger, Steffen; Kraft, Vadim; Vortmann, Britta; Rothermel, Sergej; Winter, Martin; Nowak, Sascha

2015-10-26

Shredding of the cells is often the first step in lithium-ion battery (LIB) recycling. Thus, LiNi1/3 Mn1/3 Co1/3 O2 (NMC)/graphite lithium-ion cells from a field-tested electric vehicle were shredded and transferred to tinplate or plastic storage containers. The formation of hazardous compounds within, and being released from, these containers was monitored over 20 months. The tinplate cans underwent fast corrosion as a result of either residual charge in the active battery material, which could not fully be discharged because of contact loss to the current collector, or redox reactions between the tinplate surface and metal parts of the shredded material. The headspace compositions of the containers were investigated at room temperature and 150 °C using headspace-gas chromatography-mass spectrometry (HS-GC-MS). Samples of the waste material were also collected using microwave-assisted extraction and the extracts were analyzed over a period of 20 months using ion chromatography-electrospray ionization-mass spectrometry (IC-ESI-MS). LiPF6 was identified as a conducting salt, whereas dimethyl carbonate, ethyl methyl carbonate, and ethylene carbonate were the main solvent components. Cyclohexylbenzene was also detected, which is an additive for overcharge protection. Diethyl carbonate, fluoride, difluorophosphate and several ionic and non-ionic alkyl (fluoro)phosphates were also identified. Importantly, dimethyl fluorophosphate (DMFP) and diethyl fluorophosphate (DEFP) were quantified using HS-GC-MS through the use of an internal standard. DMFP, DEFP, and related compounds are known as chemical warfare agents, and the presence of these materials is of great interest. In the case of this study, these hazardous materials are present but in manageable low concentrations. Nonetheless, the presence of such compounds and their potential release during an accident that may occur during shredding or recycling of large amounts of LIB waste should be considered. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring the influence of iron substitution in lithium rich layered oxides Li 2Ru 1–xFe xO 3: triggering the anionic redox reaction

DOE PAGES

Satish, Rohit; Lim, Kipil; Bucher, Nicolas; ...

2017-06-23

Lithium rich layered materials are an interesting class of materials which exploit both anionic and cationic redox reactions to store energy upwards of 250 mA h g –1. This paper aims to understand the nature of the redox reactions taking place in these compounds. Li 2RuO 3 was used as the base compound, which is then compared with compounds generated by partially substituting Ru with Ti and Fe respectively. Electrochemical tests indicate that Fe substitution in the sample leads to an improvement in capacity, cycle life and reduction of potential decay. To elucidate the reason for this improvement in operandomore » diffraction experiments were carried out, highlighting the formation of a secondary de-lithiated phase. The distortion of the pristine structure eventually induces frontier orbital reorganization leading to the oxygen redox reaction resulting in extra capacity. Local changes at Fe and Ru ions are recorded using in operando X-ray absorption spectroscopy (XAS). It was noted that while Ru undergoes a reversible redox reaction, Fe undergoes a significant irreversible change in its coordination environment during cycling. In conclusion, the changes in the coordination environment of oxygen and formation of O 2 n– type species were probed in situ using soft X-rays.« less

Hydrogen storage in lithium hydride: A theoretical approach

NASA Astrophysics Data System (ADS)

Banger, Suman; Nayak, Vikas; Verma, U. P.

2018-04-01

First principles calculations have been carried out to analyze structural stability of lithium hydride (LiH) in NaCl phase using the full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory (DFT). Calculations have been extended to physiosorbed H-atom compounds LiH·H2, LiH·3H2 and LiH·4H2. The obtained results are discussed in the paper. The results for LiH are in excellent agreement with earlier reported data. The obtained direct energy band gap of LiH is 3.0 eV which is in excellent agreement with earlier reported theoretical band gap. The electronic band structure plots of the hydrogen adsorbed compounds show metallic behavior. The elastic constants, anisotropy factor, shear modulus, Young's modulus, Poisson's ratio and cohesive energies of all the compounds are calculated. Calculation of the optical spectra such as the real and imaginary parts of dielectric function, optical reflectivity, absorption coefficient, optical conductivity, refractive index, extinction coefficient and electron energy loss are performed for the energy range 0-15 eV. The obtained results for LiH·H2, LiH·3H2 and LiH·4H2, are reported for the first time. This study has been made in search of materials for hydrogen storage. It is concluded that LiH is a promising material for hydrogen storage.

Ab initio and kinetic Monte Carlo study of lithium diffusion in LiSi, Li12Si7, Li13Si5 and Li15Si4

NASA Astrophysics Data System (ADS)

Moon, Janghyuk; Lee, Byeongchan; Cho, Maenghyo; Cho, Kyeongjae

2016-10-01

The kinetics of lithium atoms in various Li-Si binary compounds are investigated using density functional theory calculations and kinetic Monte Carlo calculations. The values of the Li migration energy barriers are identified by NEB calculations with vacancy-mediated, interstitial and exchange migration mechanisms in crystalline LiSi, Li12Si7, Li13Si4, and Li15Si4. A comparison of these NEB results shows that the vacancy-mediated Li migration is identified as the dominant diffusion mechanisms in Li-Si compounds. The diffusion coefficients of Li in Li-Si compounds at room temperature are determined by KMC simulation. From the KMC results, the recalculated migration energy barriers in LiSi, Li12Si7, Li13Si4, and Li15Si4 correspond to 0.306, 0.301, 0.367 and 0.320 eV, respectively. Compared to the Li migration energy barrier of 0.6 eV in crystalline Si, the drastic reduction in the Li migration energy barriers in the lithiated silicon indicates that the initial lithiation of the Si anode is the rate-limiting step. Furthermore, it is also found that Si migration is possible in Li-rich configurations. On the basis of these findings, the underlying mechanisms of kinetics on the atomic scale details are elucidated.

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

Kozikowski, Alan P.; Gunosewoyo, Hendra; Guo, Songpo

Bipolar disorder is characterized by a cycle of mania and depression, which affects approximately 5 million people in the United States. Current treatment regimes include the so-called 'mood-stabilizing drugs', such as lithium and valproate that are relatively dated drugs with various known side effects. Glycogen synthase kinase-3{beta} (GSK-3{beta}) plays a central role in regulating circadian rhythms, and lithium is known to be a direct inhibitor of GSK-3{beta}. We designed a series of second generation benzofuran-3-yl-(indol-3-yl)maleimides containing a piperidine ring that possess IC{sub 50} values in the range of 4 to 680 nM against human GSK-3{beta}. One of these compounds exhibitsmore » reasonable kinase selectivity and promising preliminary absorption, distribution, metabolism, and excretion (ADME) data. The administration of this compound at doses of 10 to 25 mg kg{sup -1} resulted in the attenuation of hyperactivity in amphetamine/chlordiazepoxide-induced manic-like mice together with enhancement of prepulse inhibition, similar to the effects found for valproate (400 mg kg{sup -1}) and the antipsychotic haloperidol (1 mg kg{sup -1}). We also tested this compound in mice carrying a mutation in the central transcriptional activator of molecular rhythms, the CLOCK gene, and found that the same compound attenuates locomotor hyperactivity in response to novelty. This study further demonstrates the use of inhibitors of GSK-3{beta} in the treatment of manic episodes of bipolar/mood disorders, thus further validating GSK-3{beta} as a relevant therapeutic target in the identification of new therapies for bipolar patients.« less

Crystal growth and characterization of europium doped lithium strontium iodide scintillator as an ionizing radiation detector

NASA Astrophysics Data System (ADS)

Uba, Samuel

High performance detectors used in the detection of ionizing radiation is critical to nuclear nonproliferation applications and other radiation detectors applications. In this research we grew and tested Europium doped Lithium Strontium Iodide compound. A mixture of lithium iodide, strontium iodide and europium iodide was used as the starting materials for this research. Congruent melting and freezing temperature of the synthesized compound was determined by differential scanning calorimetry (DSC) using a Setaram Labsys Evo DSC-DTA instrument. The melting temperatures were recorded at 390.35°C, 407.59°C and freezing temperature was recorded at 322.84°C from a graph of heat flow plotted against temperature. The synthesized material was used as the charge for the vertical Bridgeman growth, and a 6.5 cm and 7.7cm length boule were grown in a multi-zone transparent Mullen furnace. A scintillating detector of thickness 2.53mm was fabricated by mechanical lapping in mineral oil, and scintillating response and timing were obtained to a cesium source using CS-137 isotope. An energy resolution (FWHM over peak position) of 12.1% was observed for the 662keV full absorption peak. Optical absorption in the UV-Vis wavelength range was recorded for the grown crystal using a U-2900 UV/VIS Spectrophotometer. Absorption peaks were recorded at 194nm, 273nm, and 344nm from the absorbance spectrum, various optical parameters such as absorption coefficient, extinction coefficient, refractive index, and optical loss were derived. The optical band gap energy was calculated using Tauc relation expression at 1.79eV.

A rechargeable lithium battery employing cobalt chevrel-phase compound as the cathode

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

Yomaguchi, S.; Uchida, T.; Wakihara, M.

This paper reports on the single-phase region of cobalt Chevrel-phase compound (Co{sub y}Mo{sub 6}S{sub 8{minus}z}:CoCP) determined by x-ray diffraction analysis. The nonstoichiometric range of CoCP was very narrow and the only CoCP with y = 1.6,8 {minus} z = 7.7 could be prepared as a single phase. The CoCP was evaluated as a cathode for lithium secondary batteries. 1M CiClO{sub 4} in PC was used as an electrolyte. The discharge properties and discharge-charge cycling properties were measured galvanostatically under constant current densities from 0.1 to 2.0 mA/cm{sup 2}. The cell exhibited good discharge performance; for example when the cell wasmore » discharged under a cd = 0.1 mA/cm{sup 2}, 4.8 Li/Co{sub 1.6}Mo{sub 6}S{sub 7.7} were incorporated before the cell voltage fell down to 1.0 V (energy density: 277 Wh/kg). Also a rechargeability of more than 200 cycles was observed at cd = 0.5 mA/cm{sup 2}. The curve of OCV with varying Li content in the CoCP was very flat and near 2.1 V. The x-ray analysis of lithium incorporated cobalt Chevrel phase, Li{sub x}CoCP, was two sets of hexagonal lattice parameters showing the existence of two types of Chevrel phases (having different lattice parameters) coexisting in a wide range of 0 {lt} x {lt} 4.5.« less

Non-crosslinked, amorphous, block copolymer electrolyte for batteries

DOEpatents

Mayes, Anne M.; Ceder, Gerbrand; Chiang, Yet-Ming; Sadoway, Donald R.; Aydinol, Mehmet K.; Soo, Philip P.; Jang, Young-Il; Huang, Biying

2006-04-11

Solid battery components are provided. A block copolymeric electrolyte is non-crosslinked and non-glassy through the entire range of typical battery service temperatures, that is, through the entire range of at least from about 0.degree. C. to about 70.degree. C. The chains of which the copolymer is made each include at least one ionically-conductive block and at least one second block immiscible with the ionically-conductive block. The chains form an amorphous association and are arranged in an ordered nanostructure including a continuous matrix of amorphous ionically-conductive domains and amorphous second domains that are immiscible with the ionically-conductive domains. A compound is provided that has a formula of Li.sub.xM.sub.yN.sub.zO.sub.2. M and N are each metal atoms or a main group elements, and x, y and z are each numbers from about 0 to about 1. y and z are chosen such that a formal charge on the M.sub.yN.sub.z portion of the compound is (4-x). In certain embodiments, these compounds are used in the cathodes of rechargeable batteries. The present invention also includes methods of predicting the potential utility of metal dichalgogenide compounds for use in lithium intercalation compounds. It also provides methods for processing lithium intercalation oxides with the structure and compositional homogeneity necessary to realize the increased formation energies of said compounds. An article is made of a dimensionally-stable, interpenetrating microstructure of a first phase including a first component and a second phase, immiscible with the first phase, including a second component. The first and second phases define interphase boundaries between them, and at least one particle is positioned between a first phase and a second phase at an interphase boundary. When the first and second phases are electronically-conductive and ionically-conductive polymers, respectively, and the particles are ion host particles, the arrangement is an electrode of a battery.

Towards a lattice-matching solid-state battery: synthesis of a new class of lithium-ion conductors with the spinel structure.

PubMed

Rosciano, Fabio; Pescarmona, Paolo P; Houthoofd, Kristof; Persoons, Andre; Bottke, Patrick; Wilkening, Martin

2013-04-28

Lithium ion batteries have conquered most of the portable electronics market and are now on the verge of deployment in large scale applications. To be competitive in the automotive and stationary sectors, however, they must be improved in the fields of safety and energy density (W h L(-1)). Solid-state batteries with a ceramic electrolyte offer the necessary advantages to significantly improve the current state-of-the-art technology. The major limit towards realizing a practical solid-state lithium-ion battery lies in the lack of viable ceramic ionic conductors. Only a few candidate materials are available, each carrying a difficult balance between advantages and drawbacks. Here we introduce a new class of possible solid-state lithium-ion conductors with the spinel structure. Such compounds could be coupled with spinel-type electrode materials to obtain a "lattice matching" solid device where low interfacial resistance could be achieved. Powders were prepared by wet chemistry, their structure was studied by means of diffraction techniques and magic angle spinning NMR, and Li(+) self-diffusion was estimated by static NMR line shape measurements. Profound differences in the Li(+) diffusion properties were observed depending on the composition, lithium content and cationic distribution. Local Li(+) hopping in the spinel materials is accompanied by a low activation energy of circa 0.35 eV being comparable with that of, e.g., LLZO-type garnets, which represent the current benchmark in this field. We propose these novel materials as a building block for a lattice-matching all-spinel solid-state battery with low interfacial resistance.

In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles

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

Zhong, Li; Liu, Yang; Han, Wei-Qiang

Although a non-equilibrium single-phase reaction, with the absence of nucleation and growth of a second phase, is believed to be a key factor for high-rate performance of lithium-ion batteries, it is thermodynamically unfavorable and usually proceeds in electrode materials with small particle sizes (tens of nanometers). Unfortunately, the phase evolutions inside such small particles are often shrouded by the macroscopic inhomogeneous reactions of electrodes containing millions of particles, leading to intensive debate over the size-dependent microscopic reaction mechanisms. Here, we provide a generally applicable methodology based on in-situ electron diffraction study on a multi-particle system to track the lithiation pathwaysmore » in individual nanoparticles, and unambiguously reveal that lithiation of anatase TiO 2, previously long believed to be biphasic, converts to a single-phase reaction when the particle size is below ~25 nm. Our results imply the prevalence of such a size-dependent transition in lithiation mechanism among intercalation compounds whose lithium miscibility gaps are associated with a prominent size effect, and therefore provide important guidelines for designing high-power electrodes, especially cathodes.« less

In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles

DOE PAGES

Zhong, Li; Liu, Yang; Han, Wei-Qiang; ...

2017-05-05

Although a non-equilibrium single-phase reaction, with the absence of nucleation and growth of a second phase, is believed to be a key factor for high-rate performance of lithium-ion batteries, it is thermodynamically unfavorable and usually proceeds in electrode materials with small particle sizes (tens of nanometers). Unfortunately, the phase evolutions inside such small particles are often shrouded by the macroscopic inhomogeneous reactions of electrodes containing millions of particles, leading to intensive debate over the size-dependent microscopic reaction mechanisms. Here, we provide a generally applicable methodology based on in-situ electron diffraction study on a multi-particle system to track the lithiation pathwaysmore » in individual nanoparticles, and unambiguously reveal that lithiation of anatase TiO 2, previously long believed to be biphasic, converts to a single-phase reaction when the particle size is below ~25 nm. Our results imply the prevalence of such a size-dependent transition in lithiation mechanism among intercalation compounds whose lithium miscibility gaps are associated with a prominent size effect, and therefore provide important guidelines for designing high-power electrodes, especially cathodes.« less

Crystal growth, structural, optical, thermal and dielectric properties of lithium hydrogen oxalate monohydrate single crystal

NASA Astrophysics Data System (ADS)

Chandran, Senthilkumar; Paulraj, Rajesh; Ramasamy, P.

2017-11-01

The vibrational groups of the lithium hydrogen oxalate monohydrate have been investigated by FTIR and FT- Raman analyses. It has low absorbance in the UV-Vis-NIR region. The laser damage threshold study confirms that the material withstands upto 30 mJ with time of 7 s, after that circular dot damage is seen on the surface. The dark region of the surface damage spot occurs due to the thermal effects. The material is thermally stable upto 93 °C and there is no weight loss below this temperature. The dielectric studies were carried out at the frequency regions of 1 kHz-1 MHz and different temperatures from 40 °C to 80 °C. Semi-organic non-linear optical (NLO) single crystal lithium hydrogen oxalate monohydrate has been grown by slow evaporation solution growth technique. The Hirshfeld surface analysis was performed to understand the different intermolecular interactions in the title compound. The fingerprint plots contain the highest portion of H⋯O/O⋯H (48.3%) interactions.

SSH2S: Hydrogen storage in complex hydrides for an auxiliary power unit based on high temperature proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Baricco, Marcello; Bang, Mads; Fichtner, Maximilian; Hauback, Bjorn; Linder, Marc; Luetto, Carlo; Moretto, Pietro; Sgroi, Mauro

2017-02-01

The main objective of the SSH2S (Fuel Cell Coupled Solid State Hydrogen Storage Tank) project was to develop a solid state hydrogen storage tank based on complex hydrides and to fully integrate it with a High Temperature Proton Exchange Membrane (HT-PEM) fuel cell stack. A mixed lithium amide/magnesium hydride system was used as the main storage material for the tank, due to its high gravimetric storage capacity and relatively low hydrogen desorption temperature. The mixed lithium amide/magnesium hydride system was coupled with a standard intermetallic compound to take advantage of its capability to release hydrogen at ambient temperature and to ensure a fast start-up of the system. The hydrogen storage tank was designed to feed a 1 kW HT-PEM stack for 2 h to be used for an Auxiliary Power Unit (APU). A full thermal integration was possible thanks to the high operation temperature of the fuel cell and to the relative low temperature (170 °C) for hydrogen release from the mixed lithium amide/magnesium hydride system.

Organic non-aqueous cation-based redox flow batteries

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

Zhang, Lu; Huang, Jinhua; Burrell, Anthony

The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturatedmore » moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.« less

The Electrochemical Behavior in Aqueous Media of Conducting Polymers. 2. The Insoluble Fractions Obtained on the Cu(II) Catalyzed Polymerization of (2,5-Dibromo-3-Group IV Substituted) Thiophenes.

DTIC Science & Technology

1986-07-30

Grignard compounds derived from 2,5-dibromothiophene and 2,5-dibromo-3- m-thyI thiophene have been reported by Yarmamctc’ et al. (20,21). After iodine...modification of the synthetic route by employing the 2,5-dilithiothiophenes in place of the bis- Grignard compounds. Subsequent anhydrous metal salts promoted...acknowledge the Lithium Corporation for • the donation of n-butyllithium reagent . •o. , References i. G. Wagner, Angew. Chem. Int. Ed. Engi., 20 361 (1981

Tracking the Chemical and Structural Evolution of the TiS2 Electrode in the Lithium-Ion Cell Using Operando X-ray Absorption Spectroscopy.

PubMed

Zhang, Liang; Sun, Dan; Kang, Jun; Wang, Hsiao-Tsu; Hsieh, Shang-Hsien; Pong, Way-Faung; Bechtel, Hans A; Feng, Jun; Wang, Lin-Wang; Cairns, Elton J; Guo, Jinghua

2018-06-06

As the lightest and cheapest transition metal dichalcogenide, TiS 2 possesses great potential as an electrode material for lithium batteries due to the advantages of high energy density storage capability, fast ion diffusion rate, and low volume expansion. Despite the extensive investigation of its electrochemical properties, the fundamental discharge-charge reaction mechanism of the TiS 2 electrode is still elusive. Here, by a combination of ex situ and operando X-ray absorption spectroscopy with density functional theory calculations, we have clearly elucidated the evolution of the structural and chemical properties of TiS 2 during the discharge-charge processes. The lithium intercalation reaction is highly reversible and both Ti and sulfur are involved in the redox reaction during the discharge and charge processes. In contrast, the conversion reaction of TiS 2 is partially reversible in the first cycle. However, Ti-O related compounds are developed during electrochemical cycling over extended cycles, which results in the decrease of the conversion reaction reversibility and the rapid capacity fading. In addition, the solid electrolyte interphase formed on the electrode surface is found to be highly dynamic in the initial cycles and then gradually becomes more stable upon further cycling. Such understanding is important for the future design and optimization of TiS 2 based electrodes for lithium batteries.

Graphene composites as anode materials in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Mazar Atabaki, M.; Kovacevic, R.

2013-03-01

Since the world of mobile phones and laptops has significantly altered by a big designer named Steve Jobs, the electronic industries have strived to prepare smaller, thinner and lower weight products. The giant electronic companies, therefore, compete in developing more efficient hardware such as batteries used inside the small metallic or polymeric frame. One of the most important materials in the production lines is the lithium-based batteries which is so famous for its ability in recharging as many times as a user needs. However, this is not an indication of being long lasted, as many of the electronic devices are frequently being used for a long time. The performance, chemistry, safety and above all cost of the lithium ion batteries should be considered when the design of the compounds are at the top concern of the engineers. To increase the efficiency of the batteries a combination of graphene and nanoparticles is recently introduced and it has shown to have enormous technological effect in enhancing the durability of the batteries. However, due to very high electronic conductivity, these materials can be thought of as preparing the anode electrode in the lithiumion battery. In this paper, the various approaches to characterize different types of graphene/nanoparticles and the process of preparing the anode for the lithium-ion batteries as well as their electrical properties are discussed.

Fabrication and Performance of a Lithium X-Ray Lens

NASA Astrophysics Data System (ADS)

Young, Kristina; Khounsary, Ali; Jansen, Andrew N.; Dufresne, Eric M.; Nash, Philip

2007-01-01

Compound refractive lenses (CRLs) are arrays of concave lenses whose simple design and ease in implementation and alignment make them an attractive optic to focus x-rays. Factors considered in designing CRLs include lens material, fabrication, and assembly. Lithium is a desirable material because it provides the largest index of refraction decrement per unit absorption length of any solid elements. Lithium is a difficult material to handle and fabricate because it is rather malleable and more importantly, it reacts with moisture, and to a lesser extent, with oxygen and nitrogen in air. It also tends to adhere to molds and dies. We report on the fabrication and performance of a parabolic lithium lens consisting of 32 lenslets. Lenslets are fabricated in a precision press using an indenter with a parabolic profile and a 100 μm tip radius. The indenter is made of stainless steel and is figured using a computer numerically controlled (CNC) machine. The lens is designed to have a 1.7 m focal length at 10 keV energy. In an experiment conducted at the Advanced Photon Source (APS), a 0.5 mm × 0.5 mm monochromatic undulator beam strikes the lens. A focal length of 1.71, a focal spot size of 24 μm × 34 μm, and a peak intensity gain of over 18 are obtained.

Improved Ceramic Anodes for Corrosion Protection.

DTIC Science & Technology

1984-11-01

34 . 4 UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE(Whi Data Entered) BLOCK 20 (Continued) ferrite over niobium over Ni- Cr -AI-Y...plasma-sprayed lithium ferrite on a valve metal substrate. Donor doped and reduced solid sintered titanate compounds yielded electrically conductive...Traditionally. impressed current systems have used tion (CEGS) 2310. antides that are either inexpensive and very large (high silicon, chromium

High energy cathode material

DOEpatents

Li, Bin; Caldwell, Marissa; Tong, Wei; Kaye, Steven; Bhat, Vinay

2015-09-01

A composition for use in a battery electrode comprising a compound including lithium, manganese, nickel, and oxygen. The composition is characterized by a powder X-ray diffraction pattern having peaks including 18.6.+-.0.2, 35.0.+-.0.2, 36.4.+-.0.2, 37.7.+-.0.2, 42.1.+-.0.2, and 44.5.+-.0.2 degrees 2.theta. as measured using Cu K.sub..alpha. radiation.

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.

Redox shuttles for overcharge protection of lithium batteries

DOEpatents

Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

2010-12-14

The present invention is generally related to electrolytes containing novel redox shuttles for overcharge protection of lithium-ion batteries. The redox shuttles are capable of thousands hours of overcharge tolerance and have a redox potential at about 3-5.5 V vs. Li and particularly about 4.4-4.8 V vs. Li. Accordingly, in one aspect the invention provides electrolytes comprising an alkali metal salt; a polar aprotic solvent; and a redox shuttle additive that is an aromatic compound having at least one aromatic ring with four or more electronegative substituents, two or more oxygen atoms bonded to the aromatic ring, and no hydrogen atoms bonded to the aromatic ring; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

The plane-wave DFT investigations into the structure and the 11B solid-state NMR parameters of lithium fluorooxoborates

NASA Astrophysics Data System (ADS)

Czernek, Jiří; Brus, Jiří

2016-12-01

The strategy for an application of the first-principles calculations on crystalline systems to predict the 11B solid-state NMR powder-patterns is described, and its efficacy is demonstrated for two novel lithium-containing fluorooxborates, Li2B3O4F3 and Li2B6O9F2. This strategy involves the plane-wave DFT computations of the NMR parameters, whose values are then scaled and used in the spectral simulations, and are supposed to be directly applicable in the NMR crystallography studies of boron-containing systems. In particular, the GIPAW method and the PBE, PW91, and RPBE functionals are applied. Issues specific to the signal-assignment of the two compounds are also discussed.

Identification of lithium hydride and its hydrolysis products with neutron imaging

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

Garlea, Elena; King, Martin O.; Galloway, E. C.

In this study, lithium hydride (LiH) and its hydrolysis products were investigated non-destructively with neutron radiography and neutron computed tomography. Relative neutron transmission intensities (I/I 0) were measured for LiOH, Li 2O and LiH, and their linear attenuation coefficients calculated from this data. We show that 7Li is necessary for creating large differences in I/I 0 for facile identification of these compounds. The thermal decomposition of LiOH to Li 2O was also observed with neutron radiography. Computed tomography shows that the samples were fairly homogeneous, with very few macroscopic defects. Lastly, the results shown here demonstrate the feasibility of observingmore » LiH hydrolysis with neutron imaging techniques in real time.« less

Identification of lithium hydride and its hydrolysis products with neutron imaging

DOE PAGES

Garlea, Elena; King, Martin O.; Galloway, E. C.; ...

2016-12-24

In this study, lithium hydride (LiH) and its hydrolysis products were investigated non-destructively with neutron radiography and neutron computed tomography. Relative neutron transmission intensities (I/I 0) were measured for LiOH, Li 2O and LiH, and their linear attenuation coefficients calculated from this data. We show that 7Li is necessary for creating large differences in I/I 0 for facile identification of these compounds. The thermal decomposition of LiOH to Li 2O was also observed with neutron radiography. Computed tomography shows that the samples were fairly homogeneous, with very few macroscopic defects. Lastly, the results shown here demonstrate the feasibility of observingmore » LiH hydrolysis with neutron imaging techniques in real time.« less

Electric field effects on nuclear magnetic shielding of the 1:1 and 2:1 (homo and heterochiral) complexes of XOOX' (X, X' = H, CH3) with lithium cation and their chiral discrimination.

PubMed

Alkorta, Ibon; Elguero, José; Provasi, Patricio F; Pagola, Gabriel I; Ferraro, Marta B

2011-09-14

The set of 1:1 and 2:1 complexes of XOOX' (X, X' = H, CH(3)) with lithium cation has been studied to determine if they are suitable candidates for chiral discrimination in an isotropic medium via nuclear magnetic resonance spectroscopy. Conventional nuclear magnetic resonance is unable to distinguish between enantiomers in the absence of a chiral solvent. The criterion for experimental detection is valuated by the isotropic part of nuclear shielding polarisability tensors, related to a pseudoscalar of opposite sign for two enantiomers. The study includes calculations at coupled Hartree-Fock and density functional theory schemes for (17)O nucleus in each compound. Additional calculations for (1)H are also included for some compounds. A huge static homogeneous electric field, perpendicular to the magnetic field of the spectromer, as big as ≈1.7 × 10(8) V m(-1) should be applied to observe a shift of ≈1 ppm for (17)O magnetic shielding in the proposed set of complexes. © 2011 American Institute of Physics

High-pressure/high-temperature synthesis and characterization of the first palladium or platinum containing lithium transition-metal sulfides Li2M3S4 (M=Pd, Pt)

NASA Astrophysics Data System (ADS)

Heymann, Gunter; Niehaus, Oliver; Krüger, Hannes; Selter, Philipp; Brunklaus, Gunther; Pöttgen, Rainer

2016-10-01

The new lithium transition-metal sulfides Li2M3S4 (M=Pd, Pt) were obtained via multianvil high-pressure/high-temperature syntheses at 8 GPa and 1150 °C starting from a stoichiometric mixture of lithium nitride, sulfur, and palladium or platinum. Single crystal structure analyses indicated the space group P21/c (no. 14) with the following lattice parameters and refinement results: a=492.9(1), b=1005.9(2), c=614.9(2) pm, β=110.9 (1)°, R1=0.0165, wR2=0.0308 (all data) for Li2Pd3S4 and a=498.2(1), b=1005.5(2), c=613.0(2) pm, β=110.8(1)°, R1=0.0215, wR2=0.0450 (all data) for Li2Pt3S4. The crystal structures are built up from two distinct Pd/Pt sites, one of which is a special position (0,0,0), two sulfur sites, and one lithium site. The atoms Pd2/Pt2 form isolated square planar PdS4/PtS4 units, whereas the Pd1/Pt1 atoms form pairs of square planar PdS4/PtS4 units, which are connected via a common edge. These two structural motives built up a three-dimensional network structure by linking through common corners. The lithium atoms are positioned inside of the so formed channels. Li2M3S4 (M=Pd, Pt) are isostructural to the minerals jaguéite, Cu2Pd3Se4 and chrisstanleyite, Ag2Pd3Se4, which are up to now the only representatives of this structure type. Both compounds were studied with respect to their magnetic properties and can be classified as Pauli paramagnetic or diamagnetic. Regarding the possibility of lithium mobility inside the channels, of the structure, solid state 7Li NMR and high-temperature single crystal investigations revealed localization of the lithium atoms on their crystallographic sites.

Correlation and the mechanism of lithium ion diffusion with the crystal structure of Li7La3Zr2O12 revealed by an internal friction technique.

PubMed

Wang, X P; Gao, Y X; Xia, Y P; Zhuang, Z; Zhang, T; Fang, Q F

2014-04-21

The correlation and transport mechanism of lithium ions with the crystal structure of a fast lithium ion conductor Li7La3Zr2O12 are mainly investigated by internal friction (IF) and AC impedance spectroscopy techniques. Compared with the poor conductivity of tetragonal Li7La3Zr2O12, the Al stabilized cubic phase exhibits a good ionic conductivity that can be up to 1.9 × 10(-4) S cm(-1) at room temperature, which can be ascribed to the disordered distribution of lithium ions in the cubic phase. A well-pronounced relaxation IF peak (labeled as peak PC) is observed in the cubic phase while a very weak IF peak (labeled as PT) is observed in the tetragonal phase, further evidencing the difference in lithium ion migration in the two phases. Peak PC can be decomposed into two sub-peaks with the activation energy and the pre-exponential factor of relaxation time being E1 = 0.41 eV and τ01 = 1.2 × 10(-14) s for the lower temperature peak PC1 and E2 = 0.35 eV and τ02 = 1.9 × 10(-15) s for the higher temperature PC2 peak, respectively. Based on the crystalline structure of a cubic garnet-type Li7La3Zr2O12 compound, an atomistic mechanism of lithium ion diffusion via vacancies is suggested, i.e. 48g(96h) ↔ 48g(96h) for peak PC1 and 48g(96h) ↔ 24d for peak PC2, respectively. The weak PT peak in the tetragonal phase is preliminarily interpreted as due to the short jump process among neighboring octahedral sites and vacant tetrahedral sites.

Jeffamine® based polymers as highly conductive polymer electrolytes and cathode binder materials for battery application

NASA Astrophysics Data System (ADS)

Aldalur, Itziar; Zhang, Heng; Piszcz, Michał; Oteo, Uxue; Rodriguez-Martinez, Lide M.; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, Michel

2017-04-01

We report a simple synthesis route towards a new type of comb polymer material based on polyether amines oligomer side chains (i.e., Jeffamine® compounds) and a poly(ethylene-alt-maleic anhydride) backbone. Reaction proceeds by imide ring formation through the NH2 group allowing for attachment of side chains. By taking advantage of the high configurational freedoms and flexibility of propylene oxide/ethylene oxide units (PO/EO) in Jeffamine® compounds, novel polymer matrices were obtained with good elastomeric properties. Fully amorphous solid polymer electrolytes (SPEs) based on lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and Jeffamine®-based polymer matrices show low glass transition temperatures around -40 °C, high ionic conductivities and good electrochemical stabilities. The ionic conductivities of Jeffamine-based SPEs (5.3 × 10-4 S cm-1 at 70 °C and 4.5 × 10-5 S cm-1 at room temperature) are higher than those of the conventional SPEs comprising of LiTFSI and linear poly(ethylene oxide) (PEO), due to the amorphous nature and the high concentration of mobile end-groups of the Jeffamine-based polymer matrices rather than the semi-crystalline PEO The feasibility of Jeffamine-based compounds in lithium metal batteries is further demonstrated by the implementation of Jeffamine®-based polymer as a binder for cathode materials, and the stable cycling of Li|SPE|LiFePO4 and Li|SPE|S cells using Jeffamine-based SPEs.

Rational design of anode materials based on Group IVA elements (Si, Ge, and Sn) for lithium-ion batteries.

PubMed

Wu, Xing-Long; Guo, Yu-Guo; Wan, Li-Jun

2013-09-01

Lithium-ion batteries (LIBs) represent the state-of-the-art technology in rechargeable energy-storage devices and they currently occupy the prime position in the marketplace for powering an increasingly diverse range of applications. However, the fast development of these applications has led to increasing demands being placed on advanced LIBs in terms of higher energy/power densities and longer life cycles. For LIBs to meet these requirements, researchers have focused on active electrode materials, owing to their crucial roles in the electrochemical performance of batteries. For anode materials, compounds based on Group IVA (Si, Ge, and Sn) elements represent one of the directions in the development of high-capacity anodes. Although these compounds have many significant advantages when used as anode materials for LIBs, there are still some critical problems to be solved before they can meet the high requirements for practical applications. In this Focus Review, we summarize a series of rational designs for Group IVA-based anode materials, in terms of their chemical compositions and structures, that could address these problems, that is, huge volume variations during cycling, unstable surfaces/interfaces, and invalidation of transport pathways for electrons upon cycling. These designs should at least include one of the following structural benefits: 1) Contain a sufficient number of voids to accommodate the volume variations during cycling; 2) adopt a "plum-pudding"-like structure to limit the volume variations during cycling; 3) facilitate an efficient and permanent transport pathway for electrons and lithium ions; or 4) show stable surfaces/interfaces to stabilize the in situ formed SEI layers. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt Disulfide Nanoparticles Embedded in Porous Carbonaceous Micro-Polyhedrons Interlinked by Carbon Nanotubes for Superior Lithium and Sodium Storage.

PubMed

Ma, Yuan; Ma, Yanjiao; Bresser, Dominic; Ji, Yuanchun; Geiger, Dorin; Kaiser, Ute; Streb, Carsten; Varzi, Alberto; Passerini, Stefano

2018-06-27

Transition metal sulfides are appealing electrode materials for lithium and sodium batteries owing to their high theoretical capacity. However, they are commonly characterized by rather poor cycling stability and low rate capability. Herein, we investigate CoS 2 , serving as a model compound. We synthesized a porous CoS 2 /C micro-polyhedron composite entangled in a carbon-nanotube-based network (CoS 2 -C/CNT), starting from zeolitic imidazolate frameworks-67 as a single precursor. Following an efficient two-step synthesis strategy, the obtained CoS 2 nanoparticles are uniformly embedded in porous carbonaceous micro-polyhedrons, interwoven with CNTs to ensure high electronic conductivity. The CoS 2 -C/CNT nanocomposite provides excellent bifunctional energy storage performance, delivering 1030 mAh g -1 after 120 cycles and 403 mAh g -1 after 200 cycles (at 100 mA g -1 ) as electrode for lithium-ion (LIBs) and sodium-ion batteries (SIBs), respectively. In addition to these high capacities, the electrodes show outstanding rate capability and excellent long-term cycling stability with a capacity retention of 80% after 500 cycles for LIBs and 90% after 200 cycles for SIBs. In situ X-ray diffraction reveals a significant contribution of the partially graphitized carbon to the lithium and at least in part also for the sodium storage and the report of a two-step conversion reaction mechanism of CoS 2 , eventually forming metallic Co and Li 2 S/Na 2 S. Particularly the lithium storage capability at elevated (dis-)charge rates, however, appears to be substantially pseudocapacitive, thus benefiting from the highly porous nature of the nanocomposite.

A lithium-oxygen battery based on lithium superoxide.

PubMed

Lu, Jun; Lee, Yun Jung; Luo, Xiangyi; Lau, Kah Chun; Asadi, Mohammad; Wang, Hsien-Hau; Brombosz, Scott; Wen, Jianguo; Zhai, Dengyun; Chen, Zonghai; Miller, Dean J; Jeong, Yo Sub; Park, Jin-Bum; Fang, Zhigang Zak; Kumar, Bijandra; Salehi-Khojin, Amin; Sun, Yang-Kook; Curtiss, Larry A; Amine, Khalil

2016-01-21

Batteries based on sodium superoxide and on potassium superoxide have recently been reported. However, there have been no reports of a battery based on lithium superoxide (LiO2), despite much research into the lithium-oxygen (Li-O2) battery because of its potential high energy density. Several studies of Li-O2 batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2). In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime. These studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form because it is thermodynamically unstable with respect to disproportionation, giving Li2O2 (refs 19, 20). Here we show that crystalline LiO2 can be stabilized in a Li-O2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li-O2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO2, which could open the way to high-energy-density batteries based on LiO2 as well as to other possible uses of this compound, such as oxygen storage.

Alcohol-free alkoxide process for containing nuclear waste

DOEpatents

Pope, James M.; Lahoda, Edward J.

1984-01-01

Disclosed is a method of containing nuclear waste. A composition is first prepared of about 25 to about 80%, calculated as SiO.sub.2, of a partially hydrolyzed silicon compound, up to about 30%, calculated as metal oxide, of a partially hydrolyzed aluminum or calcium compound, about 5 to about 20%, calculated as metal oxide, of a partially hydrolyzed boron or calcium compound, about 3 to about 25%, calculated as metal oxide, of a partially hydrolyzed sodium, potassium or lithium compound, an alcohol in a weight ratio to hydrolyzed alkoxide of about 1.5 to about 3% and sufficient water to remove at least 99% of the alcohol as an azeotrope. The azeotrope is boiled off and up to about 40%, based on solids in the product, of the nuclear waste, is mixed into the composition. The mixture is evaporated to about 25 to about 45% solids and is melted and cooled.

Synthesis and characterization of cathode materials for lithium ion-rechargeable batteries

NASA Astrophysics Data System (ADS)

Nieto Ramos, Santander

Lithium intercalation materials are of special interest for cathodes in rechargeable lihium-ion batteries, because they are capable of reversibly intercalating lithium ions without altering the main unit. We developed a novel solution-based route for the synthesis of these lithium intercalates oxides. The first part of this work was devoted to the optimization of chemical solution process parameters in order to correlate their electrochemical properties. It was found that the lattice parameters and the crystallite size increase, whereas the lattice strain decreases with the increase in calcinations temperature. Powders annealed at 700°C for 15 h yielded best electrochemical performance. The electrochemical performance of substituted Li1.2Mn2O 4, Li1.2Mn1.8O4, Li1.2Cr 0.05Mn1.95O4, and Li1.2Cr0.05 Mn1.75O4 spinel electrodes in lithium cell has been studied. The electrochemical data showed that the Li and Cr dopant effect improves the cycleablility of spinel LiMn2O4 electrodes. The second part of this dissertation was devoted to improve the rate capabilities of these cathode materials by growing nano-size cathode particles and also by cation co-doping. Though the discharge capacity of these nano-crystalline cathodes was equivalent to their microcrystalline counterpart, these exhibited capacity fading in the 4V range. Through a combined X-ray diffraction, micro-Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) analyses, we correlated the observed capacity fading with the onset of Jahn-Teller (J-T) distortion toward the end of the discharge in the cut-off limit between 4.2 and 3.2V. It was postulated that J-T distortion is the dominant fading mechanism of these nano-crystalline cathodes then by increasing the average oxidation state of the Mn ion in a virgin lithium manganate cathode, the onset of such distortion towards the end of the discharge could be delayed, and therefore, the cycleability of these cathodes could be improved. By synthesizing lithium and aluminum ion co-doped lithium manganate particles, we could increase the average oxidation state of Mn ions in the virgin electrodes. Indeed, the cycleability of these co-doped cathodes was dramatically improved which supports our population. The third part of this thesis was devoted to synthesis and electrochemical properties of layered compounds. Lithium nickel oxides derivatives are promising positive materials for the next generation of lithium-ion batteries. Partial substitution of certain cations for nickel in this family of oxides which satisfies the demanding requirements for rechargeable battery applications. In this part the interest is focused on the effect of simultaneous cobalt as well as aluminum doping was studied to understand their effect on the phase formation behavior and electrochemical properties of solution derived lithium nickel oxide cathode materials for rechargeable batteries. (Abstract shortened by UMI.)

Functional electrolyte for lithium-ion batteries

DOEpatents

Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

2015-04-14

Functional electrolyte solvents include compounds having at least one aromatic ring with 2, 3, 4 or 5 substituents, at least one of which is a substituted or unsubstituted methoxy group, at least one of which is a tert-butyl group and at least one of which is a substituted or unsubstituted polyether or poly(ethylene oxide) (PEO) group bonded through oxygen to the aromatic ring, are provided.

Solid state 13C-NMR, infrared, X-ray powder diffraction and differential thermal studies of the homologous series of some mono-valent metal (Li, Na, K, Ag) n-alkanoates: A comparative study

NASA Astrophysics Data System (ADS)

Nelson, Peter N.; Ellis, Henry A.; White, Nicole A. S.

2015-06-01

A comparative study of the molecular packing, lattice structures and phase behaviors of the homologous series of some mono-valent metal carboxylates (Li, Na, K and Ag) is carried out via solid state FT-infrared and 13C-NMR spectroscopes, X-rays powder diffraction, density measurements, differential scanning calorimetry, polarizing light microscopy and variable temperature infrared spectroscopy. It is proposed that, for lithium, sodium and potassium carboxylates, metal-carboxyl coordination is via asymmetric chelating bidentate bonding with extensive intermolecular interactions to form tetrahedral metal centers, irrespective of chain length. However, for silver n-alkanoates, carboxyl moieties are bound to silver ions via syn-syn type bridging bidentate coordination to form dimeric units held together by extensive head group inter-molecular interactions. Furthermore, the fully extended hydrocarbon chains which are crystallized in the all-trans conformation are tilted at ca. 30°, 27°, 15° and 31° with respect to a normal to the metal plane, for lithium, sodium, silver and potassium carboxylates, respectively. All compounds are packed as lamellar bilayer structures, however, lithium compounds are crystallized in a triclinic crystal system whilst silver, sodium and potassium n-alkanoates are all monoclinic with possible P1 bravais lattice. Odd-even alternation observed in various physical features is associated with different inter-planar spacing between closely packed layers in the bilayer which are not in the same plane; a phenomenon controlled by lattice packing symmetry requirements. All compounds, except silver carboxylates, show partially reversibly first order pre-melting transitions; the number of which increases with increasing chain length. These transitions are associated, for the most part, with lamellar collapse followed by increased gauche-trans isomerism in the methylene group assembly, irrespective of chain length. It is proposed that the absence of mesomorphic transitions in their phase sequences is due to a lack of sufficient balance between attractive and repulsive electrostatic and van der Waals forces during phase change. The evidence presented in this study shows that phase behaviors of mono-valent metal carboxylates are controlled, mainly, by head group bonding.

THE REACTION OF METHYLCHLOROSILANE AND SIC14 WITH N,N’-BIS-)TRIMETHSILYL-( ETHYLENEDIAMINE

DTIC Science & Technology

B Y T REACTION OF (CH3)3SiNH(CH2)2NHSi(CH3)3 or its mono- or di-N-Lithium derivatives, respectively, and the three methylchlorosilanes and SiCl4 , the...new chain compounds ((CH3)3Si) 2N(CH2)2NHSi(CH3)3 a d ((CH )3 i 2N(CH2)2N(Si(CH3) 3)2 n 3 five-membered ring compounds wer prep re (CH ) SiNH(CH <)2NHS I CH3)3 reac s with CH3SiCl3 and SiCl4 in a complex reaction. (Author)

Luminescent Li-based metal-organic framework tailored for the selective detection of explosive nitroaromatic compounds: direct observation of interaction sites.

PubMed

Kim, Tae Kyung; Lee, Jae Hwa; Moon, Dohyun; Moon, Hoi Ri

2013-01-18

A luminescent lithium metal-organic framework (MOF) is constructed from the solvothermal reaction of Li(+) and a well-designed organic ligand, bis(4-carboxyphenyl)-N-methylamine (H(2)CPMA). A Li-based MOF can detect an explosive aromatic compound containing nitro groups as an explosophore, by showing a dramatic color change with concurrent luminescence quenching in the solid state. The detection sites are proven directly through single-crystal-to-single-crystal transformations, which show strong interactions between the aromatic rings of the electron-rich CPMA(2-) molecules and the electron-deficient nitrobenzene.

Another side of the oxazaphospholidine oxide chiral ortho-directing group.

PubMed

Martins, Nelson; Mateus, Nuno; Vinci, Daniele; Saidi, Ourida; Brigas, Amadeu; Bacsa, John; Xiao, Jianliang

2012-05-28

A new ferrocenyl oxazaphospholidine oxide 3 was synthesized together with its P-epimer 2 in the reaction of ferrocene lithium with phosphoramidite chloride 1. 3 was successfully derivatized into planar chiral 1,2-ferrocenes, including phosphine ligands, via highly diastereoselective ortho-lithiation and subsequent functionalization; these compounds display opposite planar chirality to those obtained from 2. Some of these 1,2-ferrocenes were further lithiated, allowing for the introduction of a free phosphine group at the oxazaphospholidine ring. The X-ray structures of the compounds 2 and 3 as well as those of the new 1,2-ferrocenes 4 and 7 have been determined.

Li0.5Al0.5Mg2(MoO4)3

PubMed Central

Ennajeh, Ines; Zid, Mohamed Faouzi; Driss, Ahmed

2013-01-01

The title compound, lithium/aluminium dimagnesium tetra­kis­[orthomolybdate(VI)], was prepared by a solid-state reaction route. The crystal structure is built up from MgO6 octa­hedra and MoO4 tetra­hedra sharing corners and edges, forming two types of chains running along [100]. These chains are linked into layers parallel to (010) and finally linked by MoO4 tetra­hedra into a three-dimensional framework structure with channels parallel to [001] in which lithium and aluminium cations equally occupy the same position within a distorted trigonal–bipyramidal coordination environment. The title structure is isotypic with LiMgIn(MoO4)3, with the In site becoming an Mg site and the fully occupied Li site a statistically occupied Li/Al site in the title structure. PMID:24426975

Direct catalytic cross-coupling of organolithium compounds

NASA Astrophysics Data System (ADS)

Giannerini, Massimo; Fañanás-Mastral, Martín; Feringa, Ben L.

2013-08-01

Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.

High-voltage positive electrode materials for lithium-ion batteries

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

Li, Wangda; Song, Bohang; Manthiram, Arumugam

The ever-growing demand for advanced rechargeable lithium-ion batteries in portable electronics and electric vehicles has spurred intensive research efforts over the past decade. The key to sustaining the progress in Li-ion batteries lies in the quest for safe, low-cost positive electrode (cathode) materials with desirable energy and power capabilities. One approach to boost the energy and power densities of batteries is to increase the output voltage while maintaining a high capacity, fast charge–discharge rate, and long service life. Here, this review gives an account of the various emerging high-voltage positive electrode materials that have the potential to satisfy these requirementsmore » either in the short or long term, including nickel-rich layered oxides, lithium-rich layered oxides, high-voltage spinel oxides, and high-voltage polyanionic compounds. The key barriers and the corresponding strategies for the practical viability of these cathode materials are discussed along with the optimization of electrolytes and other cell components, with a particular emphasis on recent advances in the literature. Finally, a concise perspective with respect to plausible strategies for future developments in the field is also provided.« less

Chemical Immobilization Effect on Lithium Polysulfides for Lithium-Sulfur Batteries.

PubMed

Li, Caixia; Xi, Zhucong; Guo, Dexiang; Chen, Xiangju; Yin, Longwei

2018-01-01

Despite great progress in lithium-sulfur batteries (LSBs), great obstacles still exist to achieve high loading content of sulfur and avoid the loss of active materials due to the dissolution of the intermediate polysulfide products in the electrolyte. Relationships between the intrinsic properties of nanostructured hosts and electrochemical performance of LSBs, especially, the chemical interaction effects on immobilizing polysulfides for LSB cathodes, are discussed in this Review. Moreover, the principle of rational microstructure design for LSB cathode materials with strong chemical interaction adsorbent effects on polysulfides, such as metallic compounds, metal particles, organic polymers, and heteroatom-doped carbon, is mainly described. According to the chemical immobilizing mechanism of polysulfide on LSB cathodes, three kinds of chemical immobilizing effects, including the strong chemical affinity between polar host and polar polysulfides, the chemical bonding effect between sulfur and the special function groups/atoms, and the catalytic effect on electrochemical reaction kinetics, are thoroughly reviewed. To improve the electrochemical performance and long cycling life-cycle stability of LSBs, possible solutions and strategies with respect to the rational design of the microstructure of LSB cathodes are comprehensively analyzed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural integrity--Searching the key factor to suppress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

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

Xu, Yahong; Hu, Enyuan; Yang, Feifei

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. Here, our study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. We performed combined X-ray spectroscopy, diffraction and microscopy experiments to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine lengthmore » scale morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. It also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

Structural integrity—Searching the key factor to supress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

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

Xu, Yahong; Hu, Enyuan; Yang, Feifei

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. This study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. Combined X-ray spectroscopy, diffraction and microscopy experiments are performed to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine length scalemore » morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. In conclusion, it also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

Beyond the structure-property relationship paradigm: influence of the crystal structure and microstructure on the Li+ conductivity of La2/3Li(x)Ti(1-x)Al(x)O3 Oxides.

PubMed

García-Martín, Susana; Morata-Orrantía, Ainhoa; Alario-Franco, Miguel A; Rodríguez-Carvajal, Juan; Amador, Ulises

2007-01-01

The crystal structures of several oxides of the La(2/3)Li(x)Ti(1-x)Al(x)O(3) system have been studied by selected-area electron diffraction, high-resolution transmission electron microscopy, and powder neutron diffraction, and their lithium conductivity has been by complex impedance spectroscopy. The compounds have a perovskite-related structure with a unit cell radical2 a(p)x2 a(p)x radical2 a(p) (a(p)=perovskite lattice parameter) due to the tilting of the (Ti/Al)O(6) octahedra and the ordering of lanthanum and lithium ions and vacancies along the 2 a(p) axis. The Li(+) ions present a distorted square-planar coordination and are located in interstitial positions of the structure, which could explain the very high ionic conductivity of this type of material. The lithium conductivity depends on the oxide composition and its crystal microstructure, which varies with the thermal treatment of the sample. The microstructure of these titanates is complex due to formation of domains of ordering and other defects such as strains and compositional fluctuations.

High-voltage positive electrode materials for lithium-ion batteries

DOE PAGES

Li, Wangda; Song, Bohang; Manthiram, Arumugam

2017-04-25

The ever-growing demand for advanced rechargeable lithium-ion batteries in portable electronics and electric vehicles has spurred intensive research efforts over the past decade. The key to sustaining the progress in Li-ion batteries lies in the quest for safe, low-cost positive electrode (cathode) materials with desirable energy and power capabilities. One approach to boost the energy and power densities of batteries is to increase the output voltage while maintaining a high capacity, fast charge–discharge rate, and long service life. Here, this review gives an account of the various emerging high-voltage positive electrode materials that have the potential to satisfy these requirementsmore » either in the short or long term, including nickel-rich layered oxides, lithium-rich layered oxides, high-voltage spinel oxides, and high-voltage polyanionic compounds. The key barriers and the corresponding strategies for the practical viability of these cathode materials are discussed along with the optimization of electrolytes and other cell components, with a particular emphasis on recent advances in the literature. Finally, a concise perspective with respect to plausible strategies for future developments in the field is also provided.« less

Solvent-free dry powder coating process for low-cost manufacturing of LiNi1/3Mn1/3Co1/3O2 cathodes in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Al-Shroofy, Mohanad; Zhang, Qinglin; Xu, Jiagang; Chen, Tao; Kaur, Aman Preet; Cheng, Yang-Tse

2017-06-01

We report a solvent-free dry powder coating process for making LiNi1/3Mn1/3Co1/3O2 (NMC) positive electrodes in lithium-ion batteries. This process eliminates volatile organic compound emission and reduces thermal curing time from hours to minutes. A mixture of NMC, carbon black, and poly(vinylidene difluoride) was electrostatically sprayed onto an aluminum current collector, forming a uniformly distributed electrode with controllable thickness and porosity. Charge/discharge cycling of the dry-powder-coated electrodes in lithium-ion half cells yielded a discharge specific capacity of 155 mAh g-1 and capacity retention of 80% for more than 300 cycles when the electrodes were tested between 3.0 and 4.3 V at a rate of C/5. The long-term cycling performance and durability of dry-powder coated electrodes are similar to those made by the conventional wet slurry-based method. This solvent-free dry powder coating process is a potentially lower-cost, higher-throughput, and more environmentally friendly manufacturing process compared with the conventional wet slurry-based electrode manufacturing method.

Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties

DOE PAGES

Sougrati, Moulay T.; Darwiche, Ali; Liu, Xiaohiu; ...

2016-03-16

Here we report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as a negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on 57Fe M ssbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe NCN into Li/Na NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not requiremore » heavy treatments (nanoscale tailoring, sophisticated textures, coating etc.) to obtain long cycle life with density current as high as 9 A/g -1 for hundreds of charge/discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides M x(NCN) y with M = Mn, Cr, Zn can cycle successfully versus lithium and sodium. Ultimately, their electrochemical activity and performances open the way to the design of a novel family of anode materials.« less

Structural integrity—Searching the key factor to supress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

DOE PAGES

Xu, Yahong; Hu, Enyuan; Yang, Feifei; ...

2016-08-17

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. This study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. Combined X-ray spectroscopy, diffraction and microscopy experiments are performed to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine length scalemore » morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. In conclusion, it also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

Room temperature structures and odd even behaviour of a homologous series of anhydrous lithium n-alkanoates

NASA Astrophysics Data System (ADS)

White, Nicole A. S.; Ellis, Henry A.

2008-10-01

The molecular structures of a homologous series of lithium n-alkanoates have been determined at room temperature using infrared spectroscopy, polarizing light microscopy and X-ray powder diffraction in conjunction with density and melting point measurements. For all the compounds investigated, asymmetric ionic metal-carboxylate coordination is proposed, with the molecules located within a triclinic crystal system with P1¯ space group. The molecules are nearly all of similar structure and are arranged within lamellar layers with four molecules per unit cell. The hydrocarbon chains, in nearly all trans conformation, are arranged tail-to-tail and tilted at an average angle of 55 ο to the planes containing lithium ions. The unit cell parameters such as sides: b and c increase linearly with increasing chain length whilst side a shows a linear decrease. Furthermore, the measured densities and melting points show odd-even behaviour, suggesting differences in molecular packing between odd and even chain length homologues. Geometric models are proposed to explain molecular orientation within a lamella and odd-even behaviour, involving the influence of terminal groups on the packing geometry of hydrocarbon chains within the lattice.

Polystyrene Sulfonate Threaded through a Metal-Organic Framework Membrane for Fast and Selective Lithium-Ion Separation.

PubMed

Guo, Yi; Ying, Yulong; Mao, Yiyin; Peng, Xinsheng; Chen, Banglin

2016-11-21

Extraction of lithium ions from salt-lake brines is very important to produce lithium compounds. Herein, we report a new approach to construct polystyrene sulfonate (PSS) threaded HKUST-1 metal-organic framework (MOF) membranes through an in situ confinement conversion process. The resulting membrane PSS@HKUST-1-6.7, with unique anchored three-dimensional sulfonate networks, shows a very high Li + conductivity of 5.53×10 -4  S cm -1 at 25 °C, 1.89×10 -3  S cm -1 at 70 °C, and Li + flux of 6.75 mol m -2  h -1 , which are five orders higher than that of the pristine HKUST-1 membrane. Attributed to the different size sieving effects and the affinity differences of the Li + , Na + , K + , and Mg 2+ ions to the sulfonate groups, the PSS@HKUST-1-6.7 membrane exhibits ideal selectivities of 78, 99, and 10296 for Li + /Na + , Li + /K + , Li + /Mg 2+ and real binary ion selectivities of 35, 67, and 1815, respectively, the highest ever reported among ionic conductors and Li + extraction membranes. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bulk-Type All-Solid-State Lithium-Ion Batteries: Remarkable Performances of a Carbon Nanofiber-Supported MgH2 Composite Electrode.

PubMed

Zeng, Liang; Ichikawa, Takayuki; Kawahito, Koji; Miyaoka, Hiroki; Kojima, Yoshitsugu

2017-01-25

Magnesium hydride, MgH 2 , a recently developed compound for lithium-ion batteries, is considered to be a promising conversion-type negative electrode material due to its high theoretical lithium storage capacity of over 2000 mA h g -1 , suitable working potential, and relatively small volume expansion. Nevertheless, it suffers from unsatisfactory cyclability, poor reversibility, and slow kinetics in conventional nonaqueous electrolyte systems, which greatly limit the practical application of MgH 2 . In this work, a vapor-grown carbon nanofiber was used to enhance the electrical conductivity of MgH 2 using LiBH 4 as the solid-state electrolyte. It shows that a reversible capacity of over 1200 mA h g -1 with an average voltage of 0.5 V (vs Li/Li + ) can be obtained after 50 cycles at a current density of 1000 mA g -1 . In addition, the capacity of MgH 2 retains over 1100 mA h g -1 at a high current density of 8000 mA g -1 , which indicates the possibility of using MgH 2 as a negative electrode material for high power and high capacity lithium-ion batteries in future practical applications. Moreover, the widely studied sulfide-based solid electrolyte was also used to assemble battery cells with MgH 2 electrode in the same system, and the electrochemical performance was as good as that using LiBH 4 electrolyte.

Study on the decomposition mechanism of alkyl carbonate on lithium metal by pyrolysis-gas chromatography-mass spectroscopy

NASA Astrophysics Data System (ADS)

Mogi, Ryo; Inaba, Minoru; Iriyama, Yasutoshi; Abe, Takeshi; Ogumi, Zempachi

The surface films formed on deposited lithium in electrolyte solutions based on ethylene carbonate (EC), diethyl carbonate (DEC), and dimethyl carbonate (DMC) were analyzed by pyrolysis-gas chromatography-mass spectroscopy (Py-GC-MS). In 1 M LiClO 4/EC, the main component of the surface film was easily hydrolyzed to give ethylene glycol after exposure to air, and hence was considered to have a chemical structure of ROCH 2CH 2OR', of which OR and OR' are OLi or OCO 2Li. Ethylene oxide, acetaldehyde, and 1,4-dioxane were detected in decomposition products, and they were considered to have been formed by pyrolysis of ROCH 2CH 2OR' in the pyrolyzer. The presence of ethanol in decomposition products confirmed that ring cleavage at the CH 2O bonds of EC occurs by one electron reduction. In addition, the presence of methanol implied the cleavage of the CC bond of EC upon reduction. From the surface films formed in 1 M LiClO 4/DEC and /DMC, ethanol and methanol, respectively, were detected, which suggested that corresponding lithium alkoxides and/or lithium alkyl carbonates were the main components. In 1 M LiClO 4/EC+DEC (1:1), EC dominantly decomposed to form the surface film. The surface film formed in 1 M LiPF 6/EC+DEC (1:1) contained a much smaller amount of organic compounds.

BH3-Amine and B(CH3)3-Amine Adducts as Additives for Liquid/Gel Hypergols and Solid Hybrid Rocket Motor Fuels: Property and Performance Predictions

DTIC Science & Technology

2013-12-01

and Thermolysis of Lithium, Magnesium Calcium and Strontium Tetraborate Complex Compounds With Triethylenediamine-Crystal Structure of 2BH3•C6H12N2...of Closed-Shell Atoms and Hydrides of the 1st-Row Elements. Journal of Chemical Physics 1988, 89 , 2193-2218. Petersson, G. A.; Tensfeldt, T

Extruded ceramic honeycomb and method

DOEpatents

Day, J. Paul

1995-04-04

Extruded low-expansion ceramic honeycombs comprising beta-spodumene solid solution as the principal crystal phase and with less than 7 weight percent of included mullite are produced by compounding an extrusion batch comprising a lithium aluminosilicate glass powder and a clay additive, extruding a green honeycomb body from the batch, and drying and firing the green extruded cellular honeycomb to crystallize the glass and clay into a low-expansion spodumene ceramic honeycomb body.

Capacity Fade and Its Mitigation in Li-Ion Cells with Silicon-Graphite Electrodes

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

Bareño, Javier; Shkrob, Ilya A.; Gilbert, James A.

In this study we scrutinize the causes for capacity fade in lithium-ion cells containing silicongraphite (Si-Gr) blends in the negative electrode and examine approaches for minimizing this fade. The causal mechanisms are inferred from data obtained by electrochemistry, microscopy, spectroscopy and thermogravimetry techniques. The presence of SiOxFy signals in the Si-Gr electrode, LixPOyFz compounds in the electrolyte, and SiO2 species on the NCM523 positive electrode, highlight the crucial role of hydrolytically generated HF, which accelerates the degradation of Si particles. The hydrolysis could result from residual moisture in the current electrode fabrication process, which uses aqueous binders. Water can alsomore » be released when silanol groups on the Si nanoparticles react with HF to form Si-F compounds. We note that the primary cause of capacity fade in the full cells is the loss of solid electrolyte interphase (SEI) integrity resulting from volume changes in Si particles during electrochemical cycling. Adding fluoroethylene carbonate (FEC) to the conventional electrolyte slows capacity fade through the formation of a cross linked polymer with elastomeric properties. Further gains in cell longevity are possible by excluding water during electrode fabrication, using hydrolytically stable lithium salts, and adopting electrolyte systems that provide more elasticity to the SEI layers.« less

Spectroscopic (FT-IR, FT-Raman, UV absorption, 1H and 13C NMR) and theoretical (in B3LYP/6-311++G** level) studies on alkali metal salts of caffeic acid.

PubMed

Świsłocka, Renata

2013-01-01

The effect of some metals on the electronic system of benzoic and nicotinic acids has recently been investigated by IR, Raman and UV spectroscopy [1-3]. Benzoic and nicotinic acids are regarded model systems representing a wide group of aromatic ligands which are incorporated into enzymes. In this work the FT-IR (in solid state and in solution), FT-Raman, UV absorption and (1)H and (13)C NMR spectra of caffeic acid (3,4-dihydroxycinnamic acid) and its salts with lithium, sodium, potassium, rubidium and caesium were registered, assigned and analyzed. The effect of alkali metals on the electronic system of ligands was discussed. Studies of differences in the number and position of bands from the IR, Raman, UV absorption spectra and chemical shifts from NMR spectra allowed to conclude on the distribution of electronic charge in the molecules, the delocalization energy of π electrons and the reactivity of ligands in metal complexes. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G** basis set. Bond lengths, angles and dipole moments for the optimized structures of caffeic acid and lithium, sodium, potassium caffeinates were also calculated. The theoretical wavenumbers and intensities of IR spectra were obtained. The calculated parameters were compared to the experimental characteristics of investigated compounds. Microbial activity of studied compounds was tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris. Copyright © 2012 Elsevier B.V. All rights reserved.

Solid-state structure of a Li/F carbenoid: pentafluoroethyllithium.

PubMed

Waerder, Benedikt; Steinhauer, Simon; Neumann, Beate; Stammler, Hans-Georg; Mix, Andreas; Vishnevskiy, Yury V; Hoge, Berthold; Mitzel, Norbert W

2014-10-20

Lithium carbenoids are versatile compounds for synthesis owing to their intriguing ambiphilic behavior. Although this class of compounds has been known for several years, few solid-state structures exist because of their high reactivity and often low thermal stability. Using cryo X-ray techniques, we were now able to elucidate the first solid-state structure of a Li/F alkyl carbenoid, pentafluoroethyllithium (LiC2F5), finally yielding a prototype for investigating structure-reactivity relationships for this class of molecules. The compound forms a diethyl ether-solvated dimer bridged by a rare C-F-Li link. Complementary NMR spectroscopy studies in solution show dynamic processes and indicate rapid exchange of starting material and product. Theoretical investigations help to understand the formation of the observed unusual structural motif. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of Layered Cathode Materials for Lithium-Ion Batteries

PubMed Central

Julien, Christian; Mauger, Alain; Zaghib, Karim; Groult, Henri

2016-01-01

This review presents a survey of the literature on recent progress in lithium-ion batteries, with the active sub-micron-sized particles of the positive electrode chosen in the family of lamellar compounds LiMO2, where M stands for a mixture of Ni, Mn, Co elements, and in the family of yLi2MnO3•(1 − y)LiNi½Mn½O2 layered-layered integrated materials. The structural, physical, and chemical properties of these cathode elements are reported and discussed as a function of all the synthesis parameters, which include the choice of the precursors and of the chelating agent, and as a function of the relative concentrations of the M cations and composition y. Their electrochemical properties are also reported and discussed to determine the optimum compositions in order to obtain the best electrochemical performance while maintaining the structural integrity of the electrode lattice during cycling. PMID:28773717

Template synthesis of hollow MoS2-carbon nanocomposites using microporous organic polymers and their lithium storage properties.

PubMed

Jin, Jaewon; Kim, Bolyong; Kim, Mincheol; Park, Nojin; Kang, Sungah; Lee, Sang Moon; Kim, Hae Jin; Son, Seung Uk

2015-07-14

This work shows that hollow and microporous organic polymers (H-MOPs) are good templating materials for the synthesis of inorganic material-carbon nanocomposites. The precursor compound, (NH4)2MoS4, was incorporated into H-MOPs. Heat treatment under argon resulted in the formation of hollow MoS2-carbon nanocomposites (MSC). According to microscopic analysis, the MoS2 in the MSC has a layered structure with an elongated interlayer distance. The MSC showed high reversible discharge capacities up to 802 mA h g(-1) after 30 cycles and excellent rate performance for lithium ion batteries. The promising electrochemical performance of the MSC is attributed to the very thin and disordered nature of MoS2 in the carbon skeleton. The role of chemical components of the MSC in the electrochemical process was suggested.

Mechanical and spectroscopic properties of metal-containing polyimides

NASA Technical Reports Server (NTRS)

Taylor, L. T.; St.clair, A. K.

1983-01-01

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymerization or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Thermo-luminescence and neutron absorption cross section evaluations of compounds of Lithium based oxide ceramic breeders in Li-Zr-O system

NASA Astrophysics Data System (ADS)

Mukherjee, Sumanta; Naik, Yeshwant

2018-04-01

Lithium-zirconium based oxides were prepared by combustion route. Thermal analysis (TG and DTA) was used to study the combustion process. The nucleation and growth stages were identified and their activation energies were predicted. The suitability of these oxide breeders was evaluated based on their radiation stability, variation in thermal behavior upon γ irradiation, neutron absorption and tritium breeding characteristics. Nuclear properties of these oxide ceramics were evaluated with a view to use them as efficient neutron absorbers and simultaneously breed tritium. Total neutron absorption cross sections were evaluated as a function of neutron energy in the range of 0 to 20 MeV. Resonant absorption is predicted for the neutron of energy 2.3 keV manly due to contribution from neutron induced nuclear reactions of 7Li in this energy range.

Mechanical and spectroscopic properties of metal containing polyimides

NASA Technical Reports Server (NTRS)

Taylor, L. T.; St. Clair, A. K.

1984-01-01

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymermzation or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Ab initio structure prediction of silicon and germanium sulfides for lithium-ion battery materials

NASA Astrophysics Data System (ADS)

Hsueh, Connie; Mayo, Martin; Morris, Andrew J.

Conventional experimental-based approaches to materials discovery, which can rely heavily on trial and error, are time-intensive and costly. We discuss approaches to coupling experimental and computational techniques in order to systematize, automate, and accelerate the process of materials discovery, which is of particular relevance to developing new battery materials. We use the ab initio random structure searching (AIRSS) method to conduct a systematic investigation of Si-S and Ge-S binary compounds in order to search for novel materials for lithium-ion battery (LIB) anodes. AIRSS is a high-throughput, density functional theory-based approach to structure prediction which has been successful at predicting the structures of LIBs containing sulfur and silicon and germanium. We propose a lithiation mechanism for Li-GeS2 anodes as well as report new, theoretically stable, layered and porous structures in the Si-S and Ge-S systems that pique experimental interest.

The Role of Sub- and Supercritical CO2 as "Processing Solvent" for the Recycling and Sample Preparation of Lithium Ion Battery Electrolytes.

PubMed

Nowak, Sascha; Winter, Martin

2017-03-06

Quantitative electrolyte extraction from lithium ion batteries (LIB) is of great interest for recycling processes. Following the generally valid EU legal guidelines for the recycling of batteries, 50 wt % of a LIB cell has to be recovered, which cannot be achieved without the electrolyte; hence, the electrolyte represents a target component for the recycling of LIBs. Additionally, fluoride or fluorinated compounds, as inevitably present in LIB electrolytes, can hamper or even damage recycling processes in industry and have to be removed from the solid LIB parts, as well. Finally, extraction is a necessary tool for LIB electrolyte aging analysis as well as for post-mortem investigations in general, because a qualitative overview can already be achieved after a few minutes of extraction for well-aged, apparently "dry" LIB cells, where the electrolyte is deeply penetrated or even gellified in the solid battery materials.

Structural, mechanical, electrical and optical properties of a new lithium boro phthalate NLO crystal synthesized by a slow evaporation method

NASA Astrophysics Data System (ADS)

Mohanraj, K.; Balasubramanian, D.; Jhansi, N.

2017-11-01

A new non-linear optical (NLO) single crystal of lithium boro phthalate (LiBP) was grown by slow solvent evaporation technique. The powder sample was subjected to powder X-ray diffraction (PXRD) to find its crystalline nature and the crystal structure of the grown crystal was determined using single crystal X-ray (SXRD) diffraction analysis. The Fourier Transform Infrared (FTIR) spectrum was recorded for grown crystal to identify the various functional groups present in the compound. The mechanical property of the LiBP single crystal was studied using Vickers microhardness tester. The dielectric constant and dielectric loss measurements were carried out for the grown crystal at various temperatures. The grown crystal was subjected to UV-Visible Spectral Studies to analyze the linear optical behavior of the grown crystal. The Kurtz-Perry Powder technique was employed to measure the Second Harmonic Generation efficiency of the grown crystal.

Amorphous titania/carbon composite electrode materials

DOEpatents

Vaughey, John T.; Jansen, Andrew; Joyce, Christopher D.

2017-05-09

An isolated salt comprising a compound of formula (H.sub.2X)(TiO(Y).sub.2) or a hydrate thereof, wherein X is 1,4-diazabicyclo[2.2.2]octane (DABCO), and Y is oxalate anion (C.sub.2O.sub.4.sup.-2), when heated in an oxygen-containing atmosphere at a temperature in the range of at least about 275.degree. C. to less than about 400.degree. C., decomposes to form an amorphous titania/carbon composite material comprising about 40 to about 50 percent by weight titania and about 50 to about 60 percent by weight of a carbonaceous material coating the titania. Heating the composite material at a temperature of about 400 to 500.degree. C. crystallizes the titania component to anatase. The titania materials of the invention are useful as components of the cathode or anode of a lithium or lithium ion electrochemical cell.

(5-n-Butyl-10,20-diiso­butyl­porphyrin­ato)nickel(II)

PubMed Central

Senge, Mathias O.; Dahms, Katja

2014-01-01

The asymmetric unit of the title compound, [Ni(C32H36N4)], contains two independent mol­ecules exhibiting an overall ruffled conformation of the porphyrin macrocycle and differing mainly in the positions of the methyl groups. The average Ni—N bond lengths are 1.912 (2) and 1.910 (2) Å in the two mol­ecules. The mol­ecules form a closely spaced lattice structure in which neighbouring porphyrins are oriented in a nearly perpendicular fashion to each other. The compound was prepared via nucleophilic substitution of (5,15-diiso­butyl­porphyrinato)nickel(II) with n-butyl­lithium. PMID:25161518

Light metal explosives and propellants

DOEpatents

Wood, Lowell L.; Ishikawa, Muriel Y.; Nuckolls, John H.; Pagoria, Phillip F.; Viecelli, James A.

2005-04-05

Disclosed herein are light metal explosives, pyrotechnics and propellants (LME&Ps) comprising a light metal component such as Li, B, Be or their hydrides or intermetallic compounds and alloys containing them and an oxidizer component containing a classic explosive, such as CL-20, or a non-explosive oxidizer, such as lithium perchlorate, or combinations thereof. LME&P formulations may have light metal particles and oxidizer particles ranging in size from 0.01 .mu.m to 1000 .mu.m.

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

Interfacial behavior of polymer electrolytes

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

Kerr, John; Kerr, John B.; Han, Yong Bong

2003-06-03

Evidence is presented concerning the effect of surfaces on the segmental motion of PEO-based polymer electrolytes in lithium batteries. For dry systems with no moisture the effect of surfaces of nano-particle fillers is to inhibit the segmental motion and to reduce the lithium ion transport. These effects also occur at the surfaces in composite electrodes that contain considerable quantities of carbon black nano-particles for electronic connection. The problem of reduced polymer mobility is compounded by the generation of salt concentration gradients within the composite electrode. Highly concentrated polymer electrolytes have reduced transport properties due to the increased ionic cross-linking. Combinedmore » with the interfacial interactions this leads to the generation of low mobility electrolyte layers within the electrode and to loss of capacity and power capability. It is shown that even with planar lithium metal electrodes the concentration gradients can significantly impact the interfacial impedance. The interfacial impedance of lithium/PEO-LiTFSI cells varies depending upon the time elapsed since current was turned off after polarization. The behavior is consistent with relaxation of the salt concentration gradients and indicates that a portion of the interfacial impedance usually attributed to the SEI layer is due to concentrated salt solutions next to the electrode surfaces that are very resistive. These resistive layers may undergo actual phase changes in a non-uniform manner and the possible role of the reduced mobility polymer layers in dendrite initiation and growth is also explored. It is concluded that PEO and ethylene oxide-based polymers are less than ideal with respect to this interfacial behavior.« less

The Investigation of Laser Ignited Plasma with the Application of Current Probes

NASA Astrophysics Data System (ADS)

Olsson, Trevor; Amos, James; Ujj, Laszlo

Among a variety of atomic emission spectroscopy methods Laser-induced breakdown spectroscopy (LIBS) is the one which can analyze any solid, liquid or gas sample. The elemental composition and the relative abundance of the constituent elements in the samples can be determined when the emission spectra of short laser pulses igniting plasma is then recorded and analyzed(e.g.). In our studies we have made a LIBS system which includes, but is not limited to investigating the physical phenomena and properties of the emitting plasma. Active research is going on concerning Lithium-ion batteries to increase the stored charge and energy per volume properties of the device. LIBS is proposed to test the manufacturing process and analyze the chemical constituents of the newly developed batteries. The composition of the battery itself consists of two pieces of foil, typically aluminum and copper acting as a cathode and anode respectively. Separating these two pieces of foil is a lithium based compound. The general chemical composition is Lix [Metal]y Oz where [Metal] is the specific element that is used to achieve the purpose of the battery (one metal may increase the out-put while another helps with capacity etc.). We have chosen the Li-Ion battery composed of LiCoO2 from a mobile phone in order to investigate the Stark-effect (Stark shift and Stark broadening) of the lithium present in the sample. Effects of line broadening and reabsorption of the signals are addressed by recording LIBS spectra from the powder electrolyte extracted from a Lithium-ion battery.

A comparison of the transport properties of lithium-stuffed garnets and the conventional phases Li 3Ln3Te 2O 12

NASA Astrophysics Data System (ADS)

Cussen, Edmund J.; Yip, Thomas W. S.; O'Neill, Gemma; O'Callaghan, Michael P.

2011-02-01

The structures of new phases Li 6CaLa 2Sb 2O 12 and Li 6.4Ca 1.4La 2Sb 2O 12 have been characterised using neutron powder diffraction. Rietveld analyses show that both compounds crystallise in the space group la3¯ d and contain the lithium cations in a complex arrangement with occupational disorder across oxide tetrahedra and distorted oxide octahedra, with considerable positional disorder in the latter. Variable temperature neutron diffraction experiments on Li 6.4Ca 1.4La 2Sb 2O 12 show the structure is largely invariant with only a small variation in the lithium distribution as a function of temperature. Impedance spectroscopy measurements show that the total conductivity of Li 6CaLa 2Sb 2O 12 is several orders of magnitude smaller than related lithium-stuffed garnets with σ=10 -7 S cm -1 at 95 °C and an activation energy of 0.82(3) eV. The transport properties of the conventional garnets Li 3Gd 3Te 2O 12, Li 3Tb 3Te 2O 12, Li 3Er 3Te 2O 12 and Li 3Lu 3Te 2O 12 have been evaluated and consistently show much lower values of conductivity, σ≤4.4×10 -6 S cm -1 at 285 °C and activation energies in the range 0.77(4)≤ Ea/eV≤1.21(3).

Azo compounds as a family of organic electrode materials for alkali-ion batteries.

PubMed

Luo, Chao; Borodin, Oleg; Ji, Xiao; Hou, Singyuk; Gaskell, Karen J; Fan, Xiulin; Chen, Ji; Deng, Tao; Wang, Ruixing; Jiang, Jianjun; Wang, Chunsheng

2018-02-27

Organic compounds are desirable for sustainable Li-ion batteries (LIBs), but the poor cycle stability and low power density limit their large-scale application. Here we report a family of organic compounds containing azo group (N=N) for reversible lithiation/delithiation. Azobenzene-4,4'-dicarboxylic acid lithium salt (ADALS) with an azo group in the center of the conjugated structure is used as a model azo compound to investigate the electrochemical behaviors and reaction mechanism of azo compounds. In LIBs, ADALS can provide a capacity of 190 mAh g -1 at 0.5 C (corresponding to current density of 95 mA g -1 ) and still retain 90%, 71%, and 56% of the capacity when the current density is increased to 2 C, 10 C, and 20 C, respectively. Moreover, ADALS retains 89% of initial capacity after 5,000 cycles at 20 C with a slow capacity decay rate of 0.0023% per cycle, representing one of the best performances in all organic compounds. Superior electrochemical behavior of ADALS is also observed in Na-ion batteries, demonstrating that azo compounds are universal electrode materials for alkali-ion batteries. The highly reversible redox chemistry of azo compounds to alkali ions was confirmed by density-functional theory (DFT) calculations. It provides opportunities for developing sustainable batteries.

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.

Chemical Evolution in Silicon–Graphite Composite Anodes Investigated by Vibrational Spectroscopy

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

Ruther, Rose E.; Hays, Kevin A.; An, Seong Jin

Silicon–graphite composites are under development for the next generation of high-capacity lithium-ion anodes, and vibrational spectroscopy is a powerful tool to identify the different mechanisms that contribute to performance loss. With alloy anodes, the underlying causes of cell failure are significantly different in half-cells with lithium metal counter electrodes compared to full cells with standard cathodes. However, most studies which take advantage of vibrational spectroscopy have only examined half-cells. In this work, a combination of FTIR and Raman spectroscopy describes several factors that lead to degradation in full pouch cells with LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) cathodes. The spectroscopicmore » signatures evolve after longer term cycling compared to the initial formation cycles. Several side-reactions that consume lithium ions have clear FTIR signatures, and comparison to a library of reference compounds facilitates identification. Raman microspectroscopy combined with mapping shows that the composite anodes are not homogeneous but segregate into graphite-rich and silicon-rich phases. Lithiation does not proceed uniformly either. A basis analysis of Raman maps identifies electrochemically inactive regions of the anodes. In conclusion, the spectroscopic results presented here emphasize the importance of improving electrode processing and SEI stability to enable practical composite anodes with high silicon loadings.« less

Review on anionic redox for high-capacity lithium- and sodium-ion batteries

NASA Astrophysics Data System (ADS)

Zhao, Chenglong; Wang, Qidi; Lu, Yaxiang; Hu, Yong-Sheng; Li, Baohua; Chen, Liquan

2017-05-01

Rechargeable batteries, especially lithium-ion batteries, are now widely used as power sources for portable electronics and electric vehicles, but material innovations are still needed to satisfy the increasing demand for larger energy density. Recently, lithium- and sodium-rich electrode materials, including the A2MO3-family layered compounds (A  =  Li, Na; M  =  Mn4+, Ru4+, etc), have been extensively studied as potential high-capacity electrode materials for a cumulative cationic and anionic redox activity. Negatively charged oxide ions can potentially donate electrons to compensate for the absence of oxidable transition metals as a redox center to further increase the reversible capacity. Understanding and controlling the state-of-the-art anionic redox processes is pivotal for the design of advanced energy materials, highlighted in rechargeable batteries. Hence, experimental and theoretical approaches have been developed to consecutively study the diverting processes, states, and structures involved. In this review, we attempt to present a literature overview and provide insight into the reaction mechanism with respect to the anionic redox processes, proposing some opinions as target oriented. It is hoped that, through this discussion, the search for anionic redox electrode materials with high-capacity rechargeable batteries can be advanced, and practical applications realized as soon as possible.

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.

Real-time mass spectroscopy analysis of Li-ion battery electrolyte degradation under abusive thermal conditions

NASA Astrophysics Data System (ADS)

Gaulupeau, B.; Delobel, B.; Cahen, S.; Fontana, S.; Hérold, C.

2017-02-01

The lithium-ion batteries are widely used in rechargeable electronic devices. The current challenges are to improve the capacity and safety of these systems in view of their development to a larger scale, such as for their application in electric and hybrid vehicles. Lithium-ion batteries use organic solvents because of the wide operating voltage. The corresponding electrolytes are usually based on combinations of linear, cyclic alkyl carbonates and a lithium salt such as LiPF6. It has been reported that in abusive thermal conditions, a catalytic effect of the cathode materials lead to the formation fluoro-organics compounds. In order to understand the degradation phenomenon, the study at 240 °C of the interaction between positive electrode materials (LiCoO2, LiNi1/3Mn1/3Co1/3O2, LiMn2O4 and LiFePO4) and electrolyte in dry and wet conditions has been realized by an original method which consists in analyzing by mass spectrometry in real time the volatile molecules produced. The evolution of specific gases channels coupled to the NMR reveal the formation of rarely discussed species such as 2-fluoroethanol and 1,4-dioxane. Furthermore, it appears that the presence of water or other protic impurities greatly influence their formation.

Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes.

PubMed

Godet-Bar, T; Leprêtre, J-C; Le Bacq, O; Sanchez, J-Y; Deronzier, A; Pasturel, A

2015-10-14

Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries.

Chemical Evolution in Silicon–Graphite Composite Anodes Investigated by Vibrational Spectroscopy

DOE PAGES

Ruther, Rose E.; Hays, Kevin A.; An, Seong Jin; ...

2018-05-24

Silicon–graphite composites are under development for the next generation of high-capacity lithium-ion anodes, and vibrational spectroscopy is a powerful tool to identify the different mechanisms that contribute to performance loss. With alloy anodes, the underlying causes of cell failure are significantly different in half-cells with lithium metal counter electrodes compared to full cells with standard cathodes. However, most studies which take advantage of vibrational spectroscopy have only examined half-cells. In this work, a combination of FTIR and Raman spectroscopy describes several factors that lead to degradation in full pouch cells with LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) cathodes. The spectroscopicmore » signatures evolve after longer term cycling compared to the initial formation cycles. Several side-reactions that consume lithium ions have clear FTIR signatures, and comparison to a library of reference compounds facilitates identification. Raman microspectroscopy combined with mapping shows that the composite anodes are not homogeneous but segregate into graphite-rich and silicon-rich phases. Lithiation does not proceed uniformly either. A basis analysis of Raman maps identifies electrochemically inactive regions of the anodes. In conclusion, the spectroscopic results presented here emphasize the importance of improving electrode processing and SEI stability to enable practical composite anodes with high silicon loadings.« less

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.

Mechanistic insights related to the design and construction of lithium single ion conductors

NASA Astrophysics Data System (ADS)

Spahlinger, Gregory

Lithium single ion conductors are a class of electrolytes, typically designed for lithium ion batteries, with the potential to improve the performance of these batteries. The benefits of single ion conductors arise out of the fact that their immobile anions are not capable of concentrating near the anode of the battery, causing an increase in resistance as the battery is discharged. Unfortunately lithium single ion conductors suffer severe drawbacks in their conductivity which have been attributed to diverse causes. Because of the low success rate of single ion conductors in the literature and previous work in the Baker group, I have chosen to investigate mechanistic questions related to the design and construction of these materials, without engineering new materials. An attractive design strategy for the screening of immobile anion moieties for single ion conductors would be the use of the copper catalyzed alkyne azide (CUAAC) "click" reaction in order to efficiently introduce anions onto a polymer or nanoparticle support in a way that is efficient and tunable. A variable added by this strategy would be the presence of a 1,2,3-triazole moiety which is without any significant precedent in the lithium ion electrolyte literature. In order to assess the impact of the triazole in on the conductivity of an electrolyte a series of model compounds were synthesized containing a variable number of triazoles in an otherwise poly(ethylene glycol) like oligomer chain. The model compounds were subjected to differential scanning calorimetry, electrochemical impedance spectroscopy, and in one case single crystal X-ray diffraction, and solvent shells were modeled for lithium with and without triazoles using ab initio quantum chemistry calculations. It was concluded that the triazole is not significantly stronger than an ether oxygen as a ligand in the electrolytes, however the triazole has a substantial dipole which exerts some deleterious effects on the conductivity, leading to an increase in the Arrhenius activation energy for the process. These effects are balanced by an increase in the pre-exponential factor which leads to "compensation behavior" due to the dependence of that quantity on the dipole density in the material. The observed effect is one of a lower conductivity for the model compounds relative to poly(ethylene glycol)dimethyl ether 500 at room temperature, which converges to roughly the same conductivity around 80 °C. In synthetic studies, attempts were made to synthesize N-triflylpropanesultam (TPS) a five membered heterocycle whose nucleophilic ring opening would yield a desirable anion for use in single ion conductors. TPS proved to be significantly more difficult to open than expected, which prompted a computational study. In order to study the nucleofugality of polyatomic anionic leaving groups derived from oxygen and nitrogen, a contingent of 19 methylating agents consisting of amines or alcohols activated with carbonyl or sulfonyl substituents has been examined via ab initio calculations. Gas phase activation energies for alkylation of ammonia, and gas phase methyl cation affinitys were calculated. It was found that polyatomic anionic leaving groups derived from nitrogen will have higher activation energies for Menshutkin (SN2) alkylation even when they have similar methyl cation affinities. This inherent deficit in the nucleofugality of nitrogen derived leaving groups appears to be a result of the way bond cleavage is synchronized with bond formation to the incoming ammonia nucleophile. Additionally the second sulfonyl group present in a sulfonimide appears to be less effective at activating nitrogen due to a preference for tetrahedral geometries at nitrogen in the transition states of sulfonamide groups. Optimal delocalization of electron density is therefore frustrated due to the symmetry of the leaving group.

Solid state ¹³C-NMR, infrared, X-ray powder diffraction and differential thermal studies of the homologous series of some mono-valent metal (Li, Na, K, Ag) n-alkanoates: a comparative study.

PubMed

Nelson, Peter N; Ellis, Henry A; White, Nicole A S

2015-06-15

A comparative study of the molecular packing, lattice structures and phase behaviors of the homologous series of some mono-valent metal carboxylates (Li, Na, K and Ag) is carried out via solid state FT-infrared and (13)C-NMR spectroscopes, X-rays powder diffraction, density measurements, differential scanning calorimetry, polarizing light microscopy and variable temperature infrared spectroscopy. It is proposed that, for lithium, sodium and potassium carboxylates, metal-carboxyl coordination is via asymmetric chelating bidentate bonding with extensive intermolecular interactions to form tetrahedral metal centers, irrespective of chain length. However, for silver n-alkanoates, carboxyl moieties are bound to silver ions via syn-syn type bridging bidentate coordination to form dimeric units held together by extensive head group inter-molecular interactions. Furthermore, the fully extended hydrocarbon chains which are crystallized in the all-trans conformation are tilted at ca. 30°, 27°, 15° and 31° with respect to a normal to the metal plane, for lithium, sodium, silver and potassium carboxylates, respectively. All compounds are packed as lamellar bilayer structures, however, lithium compounds are crystallized in a triclinic crystal system whilst silver, sodium and potassium n-alkanoates are all monoclinic with possible P1 bravais lattice. Odd-even alternation observed in various physical features is associated with different inter-planar spacing between closely packed layers in the bilayer which are not in the same plane; a phenomenon controlled by lattice packing symmetry requirements. All compounds, except silver carboxylates, show partially reversibly first order pre-melting transitions; the number of which increases with increasing chain length. These transitions are associated, for the most part, with lamellar collapse followed by increased gauche-trans isomerism in the methylene group assembly, irrespective of chain length. It is proposed that the absence of mesomorphic transitions in their phase sequences is due to a lack of sufficient balance between attractive and repulsive electrostatic and van der Waals forces during phase change. The evidence presented in this study shows that phase behaviors of mono-valent metal carboxylates are controlled, mainly, by head group bonding. Copyright © 2015 Elsevier B.V. All rights reserved.

Nanostructured Mo-based electrode materials for electrochemical energy storage.

PubMed

Hu, Xianluo; Zhang, Wei; Liu, Xiaoxiao; Mei, Yueni; Huang, Yunhui

2015-04-21

The development of advanced energy storage devices is at the forefront of research geared towards a sustainable future. Nanostructured materials are advantageous in offering huge surface to volume ratios, favorable transport features, and attractive physicochemical properties. They have been extensively explored in various fields of energy storage and conversion. This review is focused largely on the recent progress in nanostructured Mo-based electrode materials including molybdenum oxides (MoO(x), 2 ≤ x ≤ 3), dichalconides (MoX2, X = S, Se), and oxysalts for rechargeable lithium/sodium-ion batteries, Mg batteries, and supercapacitors. Mo-based compounds including MoO2, MoO3, MoO(3-y) (0 < y < 1), MMo(x)O(y) (M = Fe, Co, Ni, Ca, Mn, Zn, Mg, or Cd; x = 1, y = 4; x = 3, y = 8), MoS2, MoSe2, (MoO2)2P2O7, LiMoO2, Li2MoO3, etc. possess multiple valence states and exhibit rich chemistry. They are very attractive candidates for efficient electrochemical energy storage systems because of their unique physicochemical properties, such as conductivity, mechanical and thermal stability, and cyclability. In this review, we aim to provide a systematic summary of the synthesis, modification, and electrochemical performance of nanostructured Mo-based compounds, as well as their energy storage applications in lithium/sodium-ion batteries, Mg batteries, and pseudocapacitors. The relationship between nanoarchitectures and electrochemical performances as well as the related charge-storage mechanism is discussed. Moreover, remarks on the challenges and perspectives of Mo-containing compounds for further development in electrochemical energy storage applications are proposed. This review sheds light on the sustainable development of advanced rechargeable batteries and supercapacitors with nanostructured Mo-based electrode materials.

Hydrothermal synthesis and characterization of vanadyl phosphate based cathode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Chung, Youngmin

Transition metal phosphate materials have been researched as candidates for lithium-ion battery cathodes for about two decades. Among them, vanadium phosphate compounds are attractive due to their higher free energy of reaction than the corresponding iron compounds, and the greater possible change of oxidation state from V5+ to V3+. This thesis work firstly focuses on the chemical and electrochemical lithiation of epsilon--VOPO4 investigating the possibility of multi-electron intercalation. The second focus is on hydrothermal synthesis and characterization of epsilon--LiVOPO4. The hydrothermal synthesis method developed in this work produces pure epsilon-LiVOPO 4 at high temperature hydrothermal reaction and pure LiVOPO4˙2H 2O at low temperature. The first charge capacity of hydrothermal epsilon-LiVOPO 4 is around 308 mAh/g, which is almost 97% of the theoretical capacity. It also shows good reversibility in the first five cycles after which capacity fading occurs. For more detailed structural analysis of hydrothermal epsilon-LiVOPO 4, we used in-situ synchrotron XRD and EXAFS upon heating combined with TGA-MS. These techniques have revealed intercalated protons that are removed at about 350 °C, and a reversible symmetry change from triclinic to monoclinic at high temperature. Furthermore, we have used chemical lithiation with BuLi to produce and characterize epsilon-Li2VOPO 4 phase. Finally, we have modified the hydrothermal method to produce Cr-substituted epsilon--LiVOPO4 by changing the amount LiOH and adding Cr precursor. Cr substitution is found to modify the stoichiometry of the compound and to improve its cyclability at both high and low current densities.

Effect of cannabinoids on lithium-induced vomiting in the Suncus murinus (house musk shrew).

PubMed

Parker, Linda A; Kwiatkowska, Magdalena; Burton, Page; Mechoulam, Raphael

2004-01-01

Marijuana has been reported to interfere with nausea and vomiting in chemotherapy patients. The principal cannabinoids found in marijuana include the psychoactive compound Delta-9-tetrahydrocannabinol (THC) and the non-psychoactive compound cannabidiol (CBD). The experiments reported here evaluated the potential of THC and CBD to interfere with vomiting in the Suncus murinus (house musk shrew) produced by lithium chloride (LiCl), which is the most commonly employed unconditioned stimulus for taste avoidance. To evaluate the potential of the principal components of marijuana, THC and CBD, to suppress Li-induced vomiting in the house musk shrew. Shrews were injected with vehicle or one of two cannabinoids [Delta-9-THC (1-20 mg/kg), or CBD (2.5-40 mg/kg)] 10 min prior to an injection of LiCl (390 mg/kg of 0.15 M) and were then observed for 45 min. The frequency of vomiting episodes and the latency to the first episode were measured. The role of the CB1 receptor in these effects was also evaluated by pretreatment with SR-141716. Delta-9-THC produced a dose-dependent suppression of Li-induced vomiting, with higher doses producing greater suppression than lower doses. CBD produced a biphasic effect with lower doses producing suppression and higher doses producing enhancement of Li-induced vomiting. The suppression of Li-induced vomiting by THC, but not by CBD, was reversed by SR-141716. These results indicate that two major cannabinoid compounds found in marijuana, THC and CBD, are effective treatments for Li-induced vomiting; however, only THC acts by the CB1 receptor. The effects of THC and CBD on vomiting were dose dependent; with THC the effect was linear, but with CBD the effect was biphasic.

Therapeutic drug monitoring of psychotropic medications

PubMed Central

Mitchell, Philip B

2000-01-01

Therapeutic drug monitoring (TDM) of a number of psychotropic medications has proven to be of value, enabling minimization of the limitations of considerable genetic variability in their metabolism and the high rates of poor compliance with many psychiatric disorders. Therapeutic ranges have been established for lithium, some of the tricyclic antidepressants, and clozapine. TDM has also been shown to be useful in avoiding toxicity (as many psychotropics have narrow therapeutic indices), particularly that due to interactions with other compounds. PMID:10759685

A general method for the catalytic nazarov cyclization of heteroaromatic compounds.

PubMed

Malona, John A; Colbourne, Jessica M; Frontier, Alison J

2006-11-23

A general, catalytic method for efficient Nazarov cyclization of systems containing heteroaromatic components has been developed. Scandium triflate was identified as the most reactive promoter, and it was found that addition of lithium perchlorate was necessary for synthetically useful catalytic cyclizations. The method was used to synthesize a range of cyclopentanone-fused heteroaromatic systems in 36-97% yield, and the reactivity trends observed demonstrate the impact of polarization on cyclization efficiency. [reaction: see text].

Electrical conductivity and thermoelectric power of La1- x Li x CoO3-δ (0 ≤ x ≤ 0.1) oxides

NASA Astrophysics Data System (ADS)

Vecherskii, S. I.; Konopel'ko, M. A.; Batalov, N. N.; Antonov, B. D.; Reznitskikh, O. G.; Yaroslavtseva, T. V.

2016-12-01

The influence of the concentration of lithium ions on the phase composition, the electrical conductivity, and the thermoelectric power of La1- x Li x CoO3-δ (0 ≤ x ≤ 0.1) oxides synthesized by the ceramic method has been investigated. It has been found that the region of the existence of perovskite-type La1- x Li x CoO3-δ solid solutions does not exceed x = 0.05. The doping with lithium leads to an increase in the electrical conductivity of single-phase samples in comparison with that of the LaCoO3 compound. As the temperature increases from 300 to 400 K, the thermoelectric power of the LaCoO3 compound increases from the negative to positive values and then decreases, but remains positive in the temperature range from 400 to 1020 K. The thermoelectric power of the other samples has a positive sign. The results obtained have been discussed based on the models of the electron density of states in LaCoO3 and La1- x Sr x CoO3-δ, proposed in the studies of Señarís-Rodríguez and Goodenough, as well as in the framework of the theory of non-crystalline materials, developed by Mott.

Anion-Tunable Properties and Electrochemical Performance of Functionalized Ferrocene Compounds

NASA Astrophysics Data System (ADS)

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M.; Xu, Wu; Helm, Monte L.; Burton, Sarah D.; Sorensen, Christina M.; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-09-01

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Finally, the electrochemical performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability.

Anion-Tunable Properties and Electrochemical Performance of Functionalized Ferrocene Compounds.

PubMed

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M; Xu, Wu; Helm, Monte L; Burton, Sarah D; Sorensen, Christina M; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-09-16

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Finally, the electrochemical performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability.

The importance of transport property studies for battery electrolytes: revisiting the transport properties of lithium-N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide mixtures.

PubMed

Rüther, Thomas; Kanakubo, Mitsuhiro; Best, Adam S; Harris, Kenneth R

2017-04-19

Transport properties are examined in some detail for samples of the low temperature molten salt N-propyl-N-methyl pyrrolidinium bis(fluorosulfonyl)imide [Pyr 13 ][FSI] from two different commercial suppliers. A similar set of data is presented for two different concentrations of binary lithium-[Pyr 13 ][FSI] salt mixtures from one supplier. A new and significantly different production process is used for the synthesis of Li[FSI] as well as the [Pyr 13 ] + salt used in the mixtures. Results for the viscosity, conductivity, and self-diffusion coefficients, together with the density and expansivity and apparent molar volume, are reported over the temperature range of (0 to 80) °C. The data for neat [Pyr 13 ][FSI] are discussed in the context of velocity cross correlation (VCC or f ij ) and Laity resistance (r ij ) coefficients. Unusually, f +- ∼ f ++ < f -- . The three resistance coefficients are of similar magnitude indicating all three ion-ion interactions contribute to the transport properties, not just the cation-anion interaction. The composition dependence of the transport properties is compared to previously reported data for the same and related compounds: in contrast to high-temperature molten salt mixtures, this is an exponential dependence. The Nernst-Einstein parameter Δ, which contains information on the correlations of the ionic velocities and is determined by differences in the VCC for the various ion-ion combinations, was calculated for both the neat ionic liquid and its binary mixture. It increases with increasing lithium concentration. The new data set also allows some conclusions with regards to the lithium-[FSI] - coordination environment.

Method of solubilizing phthalocyanines and metallophthalocyanines

DOEpatents

Rathke, Jerome W.; Chen, Michael J.; Fendrick, Carol M.

1997-11-04

A one-step method of manufacturing soluble phthalocyanines and metallophthalocyanines, like zinc phthalocyanine, by converting a phthalocyanine or a metallophthalocyanine to a trialkylsilyl-substituted derivative is disclosed. The phthalocyanine or metallophthalocyanine is converted to a soluble trialkylsilyl-substituted derivative by interacting the phthalocyanine or metallophthalocyanine with an active metal amide, like lithium 2,2,6,6-tetramethylpiperidide, and a halotrialkylsilane, like chlorotrimethylsilane, to provide a phthalocyanine compound, like phthalocyanine monomers, dimers or polymers, metalated or unmetalated, that are soluble in organic media.

Method of solubilizing phthalocyanines and metallophthalocyanines

DOEpatents

Rathke, Jerome W.; Chen, Michael J.; Fendrick, Carol M.

1997-01-01

A one-step method of manufacturing soluble phthalocyanines and metallophthalocyanines, like zinc phthalocyanine, by converting a phthalocyanine or a metallophthalocyanine to a trialkylsilyl-substituted derivative is disclosed. The phthalocyanine or metallophthalocyanine is converted to a soluble trialkylsilyl-substituted derivative by interacting the phthalocyanine or metallophthalocyanine with an active metal amide, like lithium 2,2,6,6-tetramethylpiperidide, and a halotrialkylsilane, like chlorotrimethylsilane, to provide a phthalocyanine compound, like phthalocyanine monomers, dimers or polymers, metalated or unmetalated, that are soluble in organic media.

Study of the Deposition of Ammonium Perchlorate Following the Static Firing of MK-58 Rocket Motors

DTIC Science & Technology

2008-10-01

hyperthyroidism , gas generators, electrolytes for lithium cells, and as chemical reagents. The occurrence of perchlorate in the environment is...contain 19.6 kg of cross-linked double based propellants, with 7.8 % by weight of binder, 62 % of RDX, 25.88 % of plasticizers, and a few percent...compound is present at less than 1% by weight in the propellant but it might be considered as a health hazard since it has adverse toxicological impacts

Perspectives on Computational Organic Chemistry

PubMed Central

Streitwieser, Andrew

2009-01-01

The author reviews how his early love for theoretical organic chemistry led to experimental research and the extended search for quantitative correlations between experiment and quantum calculations. The experimental work led to ion pair acidities of alkali-organic compounds and most recently to equilibria and reactions of lithium and cesium enolates in THF. This chemistry is now being modeled by ab initio calculations. An important consideration is the treatment of solvation in which coordination of the alkali cation with the ether solvent plays a major role. PMID:19518150

Redox shuttles for lithium ion batteries

DOEpatents

Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

2016-03-22

An electrolyte may include compounds of general Formula IVA or IVB. ##STR00001## where, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 are each independently selected from H, F, Cl, Br, CN, NO.sub.2, alkyl, haloalkyl, and alkoxy groups; X and Y are each independently O, S, N, or P; and Z' is a linkage between X and Y, and at least one of R.sup.8, R.sup.9, R.sup.10, and R.sup.11 is other than H.

Electrochemical behavior of Al in a non-aqueous alkyl carbonate solution containing LiBOB salt

NASA Astrophysics Data System (ADS)

Myung, Seung-Taek; Natsui, Hiroshi; Sun, Yang-Kook; Yashiro, Hitoshi

Aluminum was studied as a current collector for rechargeable lithium batteries to understand electrochemical and passivation behavior. Electrochemical polarization tests, in situ scratch polarization tests and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) analysis in lithium bis-oxalato borate (LiBOB)-containing alkyl carbonate solution were conducted. The Al foil did not follow the alloy and de-alloy process with the LiBOB salt in electrolyte at 0 V vs. Li/Li + in the cathodic sweep. During the anodic scan to the noble direction, the absence of an oxidation peak up to 3 V vs. Li/Li + indicated that the air-formed oxide layer of Al was not reduced to metal. Oxide-free Al surfaces made by the in situ scratch test during the electrochemical polarization resulted in abrupt alloy formation with Li at 0 V vs. Li/Li +, but the newly formed surface formed passive films at higher potential with oxygen, namely, Al-O compound, as confirmed by ToF-SIMS.

Boron Neutron Capture Therapy - A Literature Review

PubMed Central

Nedunchezhian, Kavitaa; Thiruppathy, Manigandan; Thirugnanamurthy, Sarumathi

2016-01-01

Boron Neutron Capture Therapy (BNCT) is a radiation science which is emerging as a hopeful tool in treating cancer, by selectively concentrating boron compounds in tumour cells and then subjecting the tumour cells to epithermal neutron beam radiation. BNCT bestows upon the nuclear reaction that occurs when Boron-10, a stable isotope, is irradiated with low-energy thermal neutrons to yield α particles (Helium-4) and recoiling lithium-7 nuclei. A large number of 10 Boron (10B) atoms have to be localized on or within neoplastic cells for BNCT to be effective, and an adequate number of thermal neutrons have to be absorbed by the 10B atoms to maintain a lethal 10B (n, α) lithium-7 reaction. The most exclusive property of BNCT is that it can deposit an immense dose gradient between the tumour cells and normal cells. BNCT integrates the fundamental focusing perception of chemotherapy and the gross anatomical localization proposition of traditional radiotherapy. PMID:28209015

Reversible Phase Transition with Ultralarge Dielectric Relaxation Behaviors in Succinimide Lithium(I) Hybrids.

PubMed

Tang, Yun-Zhi; Wang, Bin; Zhou, Hai-Tao; Chen, Shao-Peng; Tan, Yu-Hui; Wang, Chang-Feng; Yang, Chang-Shan; Wen, He-Rui

2018-02-05

Dielectric relaxations have widely applied on high permittivity capacitors, dielectric switches, ferroelectrics, pyroelectrics, and electrical insulating materials. However, few investigations of large dielectric relaxation behaviors on organic-inorganic hybrid materials have been documented before. Here we present a novel two-dimensional succinimide lithium(I) hybrid compound, [Li(PDD) 2 ClO 4 ] n , 1, (PDD = 2,5-pyrrolidinedione = succinimide) which shows reversible phase transition behavior in the vicinity of 228 K accompanied by an unusual symmetry breaking from I4 1 /amd to C2/c. X-ray single crystal diffractions analysis indicates the twist motion of pyrrolidine heterocycles, and order-disorder motion of ClO 4 - anions triggered the reversible phase transition. By means of an intuitive crystallographic model (rattling ion model), we further illustrated the mechanism of the interesting reversible phase transition. Particularly, 1 shows ultralarge dielectric relaxation behavior in the vicinity of the phase transition by its dielectric constant dependence on temperatures and frequencies as well as its Cole-Cole relation.

Metallic Li colloids studied by Li-7 MAS NMR in electron-irradiated LiF

NASA Astrophysics Data System (ADS)

Zogal, O. J.; Beuneu, F.; Vajda, P.; Florian, P.; Massiot, D.

Li-7 MAS NMR spectra of 2.5 MeV electron-irradiated LiF crystals have been measured in a field of 9.4 T. Besides the resonance line of the ionic compound, a second well-separated spectrum is observed in the region of the Knight shift value for metallic lithium. At room temperature, the latter can be decomposed into two components with different Knight shift and linewidth values. When the temperature is increased, line narrowing takes place at first, indicating shortening of correlation times for self-diffusion, independently in both components. Above 370 K, both lines broaden and approach each other before collapsing into a single line. The high ppm component disappears after crossing the melting temperature of metallic lithium (454 K). The two lines are attributed to different types of metallic Li: one to bulk-like metal, the other to Li present initially under pressure and relaxing to the former under thermal treatment.

Synthesis, Characterization, and Electrochemical Behavior of LiMnxFe(1−x)PO4 Composites Obtained from Phenylphosphonate-Based Organic-Inorganic Hybrids

PubMed Central

Dell’Era, Alessandro; Pasquali, Mauro; Bauer, Elvira Maria; Lupi, Carla

2017-01-01

The synthesis of organic-inorganic hybrid compounds based on phenylphosphonate and their use as precursors to form LiMnxFe(1−x)PO4 composites containing carbonaceous substances with sub-micrometric morphology are presented. The experimental procedure includes the preliminary synthesis of Fe2+ and/or Mn2+ phenylphosphonates with the general formula Fe(1−x)Mnx[(C6H5PO3)(H2O)] (with 0 < x < 1), which are then mixed at different molar ratios with lithium carbonate. In this way the carbon, obtained from in situ partial oxidation of the precursor organic part, coats the LiMnxFe(1−x)PO4 particles. After a structural and morphological characterization, the electrochemical behavior of lithium iron manganese phosphates has been compared to the one of pristine LiFePO4 and LiMnPO4, in order to evaluate the doping influence on the material. PMID:29301206

Biomass Waste Inspired Highly Porous Carbon for High Performance Lithium/Sulfur Batteries

PubMed Central

Zhao, Yan; Ren, Jun; Tan, Taizhe; Babaa, Moulay-Rachid; Bakenov, Zhumabay; Liu, Ning; Zhang, Yongguang

2017-01-01

The synthesis of highly porous carbon (HPC) materials from poplar catkin by KOH chemical activation and hydrothermal carbonization as a conductive additive to a lithium-sulfur cathode is reported. Elemental sulfur was composited with as-prepared HPC through a melt diffusion method to form a S/HPC nanocomposite. Structure and morphology characterization revealed a hierarchically sponge-like structure of HPC with high pore volume (0.62 cm3∙g−1) and large specific surface area (1261.7 m2∙g−1). When tested in Li/S batteries, the resulting compound demonstrated excellent cycling stability, delivering a second-specific capacity of 1154 mAh∙g−1 as well as presenting 74% retention of value after 100 cycles at 0.1 C. Therefore, the porous structure of HPC plays an important role in enhancing electrochemical properties, which provides conditions for effective charge transfer and effective trapping of soluble polysulfide intermediates, and remarkably improves the electrochemical performance of S/HPC composite cathodes. PMID:28878149

Ternary metal fluorides as high-energy cathodes with low cycling hysteresis

PubMed Central

Wang, Feng; Kim, Sung-Wook; Seo, Dong-Hwa; Kang, Kisuk; Wang, Liping; Su, Dong; Vajo, John J.; Wang, John; Graetz, Jason

2015-01-01

Transition metal fluorides are an appealing alternative to conventional intercalation compounds for use as cathodes in next-generation lithium batteries due to their extremely high capacity (3–4 times greater than the current state-of-the-art). However, issues related to reversibility, energy efficiency and kinetics prevent their practical application. Here we report on the synthesis, structural and electrochemical properties of ternary metal fluorides (M1yM21-yFx: M1, M2=Fe, Cu), which may overcome these issues. By substituting Cu into the Fe lattice, forming the solid–solution CuyFe1-yF2, reversible Cu and Fe redox reactions are achieved with surprisingly small hysteresis (<150 mV). This finding indicates that cation substitution may provide a new avenue for tailoring key electrochemical properties of conversion electrodes. Although the reversible capacity of Cu conversion fades rapidly, likely due to Cu+ dissolution, the low hysteresis and high energy suggest that a Cu-based fluoride cathode remains an intriguing candidate for rechargeable lithium batteries. PMID:25808876

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

NASA Astrophysics Data System (ADS)

Chen, Zhenlian; Li, Jun

2013-03-01

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

Chemical weathering of layered Ni-rich oxide electrode materials: Evidence for cation exchange

DOE PAGES

Shkrob, Ilya A.; Gilbert, James A.; Phillips, Patrick J.; ...

2017-05-13

Lithiated ternary oxides containing nickel, cobalt, and manganese are intercalation compounds that are used as positive electrodes in high-energy lithium-ion batteries. These materials undergo compositional changes that adversely affect their cycling performance when they are stored in humid air or exposed to moisture. There is a new urgency to better understanding of these “weathering” processes as manufacturing moves towards a more environmentally benign aqueous processing of the positive electrode. Delithiation in the oxide subsurface regions and the formation of lithium salts (such as hydroxides and carbonates) coating the surface, have been suggested as chemical drivers for these processes, but themore » mechanistic details remain poorly known. The redox reactions which follow oxide delithiation are believed to cause all of the observed transformations. In this article we suggest another possibility: namely, the proton – lithium exchange. We argue that this hypothesis provides a simple, comprehensive rationale for our observations from X-ray diffraction, X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and electrochemical measurements. These observations include contraction of the c-axis (unit cell) lattice parameter, strain in the crystalline oxide bulk, directionality of the chemical damage, formation of amorphous surface films, and the partial recovery of capacity loss by electrochemical relithiation of the material. Lastly, these effects need to be mitigated before aqueous processing of the positive electrode can find widespread adoption during cell manufacturing.« less

Investigation on the fly ash thermal treatment on the performance of Lithium Ferriphosphate (LiFePO{sub 4}) battery

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

Febiolita, Bella; Khoirunnissak, Dewi; Purwanto, Agus, E-mail: aguspurw@gmail.com

Addition of the fly ash can be used to improve the capacity of LiFePO{sub 4} battery. Fly ash was added in Acethylene Black (AB) as 2% of the total weight of Acetylene Black (AB). The effects of temperature variation and fly ash characteristics were analyzed. Fly ash was prepared by heating at 50, 100, 150, and 250°C in muffle furnace for 5 hours and passed in 200 mesh screen prior to mixing it with other compounds. Lithium Ferriphospat (LiFePO{sub 4}), fly ash, Acethylene Black (AB), Polyvinylidene Fluoride (PVDF) as a binder and N-methyl-2-pyrrolidone (NMP) as a solvent were mixed tomore » be slurry. The slurry were coated, dried and hot pressed to make a cathode film. The performance of battery lithium was examined by eight channel battery analyzer. The composition of the fly ash was examined by X-ray fluorescence spectrometry (XRF) and Fourier Tansform Infrared Spectroscopy (FTIR). The excellent performance was shown in the fly ash addition which were treated by heating at 150°C. The capacity of fly ash added LiFePO{sub 4} battery is 94.373 mAh/g, which is higher than that of without fly ash addition, i.e. 67.998 mAh/g.« less

Advanced and safer lithium-ion battery based on sustainable electrodes

NASA Astrophysics Data System (ADS)

Ding, Xiang; Huang, Xiaobing; Jin, Junling; Ming, Hai; Wang, Limin; Ming, Jun

2018-03-01

Seeking advanced and safer lithium-ion battery with sustainable characteristic is significant for the development of electronic devices and electric vehicles. Herein, a new porous TiO2 nanobundles (PTNBs) is synthesized though a scalable and green hydrothermal strategy from the TiO2 powders without using any high-cost and harmful organic titanium-based compounds. The PTNBs exhibits an extremely high lithium storage capacity of 296 mAh g-1 at 100 mA g-1, where the capacity can maintain over 146 mAh g-1 even after 500 cycles at 1000 mA g-1. To pursue more reliable Li-ion batteries, full batteries of PTNBs/LiNixMn1-xO4 (x = 0, 0.5) using spinel structured cathode are constructed. The batteries have the features of sustainability and deliver high capacities of 112 mAh gcathode-1 and 102 mAh gcathode-1 with stable capacity retentions of 99% and 90% over 140 cycles. Note that the energy densities can achieve as high as 267 and 270 Wh kgcathode-1 (535 and 540 Wh kganode-1) respectively, which is feasible to satisfy diverse requirements for energy storage products. We believe that the universal synthetic strategy, appealing structure and intriguing properties of PTNBs is applicable for wider applications, while the concept of sustainable strategy seeking reliable and safer Li-ion battery can attract broad interest.

Synthesis and crystal structure of LiCuFe{sub 2}(VO{sub 4}){sub 3} by Rietveld method

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

Belik, A.A.

1999-10-01

A new triple vanadate LiCuFe{sub 2}(VO{sub 4}){sub 3} was synthesized by a solid-state method. The compound is isotypic with mineral howardevansite, NaCuFe{sub 2}(VO{sub 4}){sub 3}, and crystallizes in a triclinic system (space group P{bar 1} (No. 2); a = 8.1484(5), b = 9.8024(7), c = 6.6355(4) {angstrom}, {alpha} = 103.832(3), {beta} = 102.353(3), {gamma} = 106.975(3), V = 468.68 {angstrom}{sup 3}, Z = 2). Crystal structure of LiCuFe{sub 2}(VO{sub 4}){sub 3} was refined by Rietveld method with R{sub WP} = 2.32%, R{sub P} = 1.76%, R{sub I} = 2.82%, S = 1.55, using X-ray diffraction. The crystal structure has fivemore » independent cation sites. Lithium cations are located in the cavities M(1)O{sub 6} and M(5)O{sub 10}, which form infinite chains in the [001] direction and are linked through a common face. The lithium cation in the M(1)O{sub 6} cavity has a square planar coordination. The lithium cation in the M(5)O{sub 10} cavity is strongly displaced up to 1.2 {angstrom} from the special position (0, 0, 0.5) to a half-occupied general position (0.037, 0.087, 0.40).« less

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

Shkrob, Ilya A.; Gilbert, James A.; Phillips, Patrick J.

Lithiated ternary oxides containing nickel, cobalt, and manganese are intercalation compounds that are used as positive electrodes in high-energy lithium-ion batteries. These materials undergo compositional changes that adversely affect their cycling performance when they are stored in humid air or exposed to moisture. There is a new urgency to better understanding of these “weathering” processes as manufacturing moves towards a more environmentally benign aqueous processing of the positive electrode. Delithiation in the oxide subsurface regions and the formation of lithium salts (such as hydroxides and carbonates) coating the surface, have been suggested as chemical drivers for these processes, but themore » mechanistic details remain poorly known. The redox reactions which follow oxide delithiation are believed to cause all of the observed transformations. In this article we suggest another possibility: namely, the proton – lithium exchange. We argue that this hypothesis provides a simple, comprehensive rationale for our observations from X-ray diffraction, X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and electrochemical measurements. These observations include contraction of the c-axis (unit cell) lattice parameter, strain in the crystalline oxide bulk, directionality of the chemical damage, formation of amorphous surface films, and the partial recovery of capacity loss by electrochemical relithiation of the material. Lastly, these effects need to be mitigated before aqueous processing of the positive electrode can find widespread adoption during cell manufacturing.« less

Four-electron transfer tandem tetracyanoquinodimethane for cathode-active material in lithium secondary battery

NASA Astrophysics Data System (ADS)

Kurimoto, Naoya; Omoda, Ryo; Mizumo, Tomonobu; Ito, Seitaro; Aihara, Yuichi; Itoh, Takahito

2018-02-01

Quinoid compounds are important candidates of organic active materials for lithium-ion batteries. However, its high solubility to organic electrolyte solutions and low redox potential are known as their major drawbacks. To circumvent these issues, we have designed and synthesized a tandem-tetracyanoquinonedimethane type cathode-active material, 11,11,12,12,13,13,14,14-octacyano-1,4,5,8-anthradiquinotetramethane (OCNAQ), that has four redox sites per molecule, high redox potential and suppressed solubility to electrolyte solution. Synthesized OCNAQ has been found to have two-step redox reactions by cyclic voltammetry, and each step consists of two-electron reactions. During charge-discharge tests using selected organic cathode-active materials with a lithium metal anode, the cell voltages obtained from OCNAQ are higher than those for 11,11-dicyanoanthraquinone methide (AQM) as expected, due to the strong electron-withdrawing effect of the cyano groups. Unfortunately, even with the use of the organic active material, the issue of dissolution to the electrolyte solution cannot be suppressed completely; however, appropriate choice of the electrolyte solutions, glyme-based electrolyte solutions in this study, give considerable improvement of the cycle retention (98% and 56% at 10 and 100 cycles at 0.5C, respectively). The specific capacity and energy density obtained in this study are 206 mAh g-1 and 554 mWh g-1 with respect to the cathode active material.

Oxide Fiber Cathode Materials for Rechargeable Lithium Cells

NASA Technical Reports Server (NTRS)

Rice, Catherine E.; Welker, Mark F.

2008-01-01

LiCoO2 and LiNiO2 fibers have been investigated as alternatives to LiCoO2 and LiNiO2 powders used as lithium-intercalation compounds in cathodes of rechargeable lithium-ion electrochemical cells. In making such a cathode, LiCoO2 or LiNiO2 powder is mixed with a binder [e.g., poly(vinylidene fluoride)] and an electrically conductive additive (usually carbon) and the mixture is pressed to form a disk. The binder and conductive additive contribute weight and volume, reducing the specific energy and energy density, respectively. In contrast, LiCoO2 or LiNiO2 fibers can be pressed and sintered to form a cathode, without need for a binder or a conductive additive. The inter-grain contacts of the fibers are stronger and have fewer defects than do those of powder particles. These characteristics translate to increased flexibility and greater resilience on cycling and, consequently, to reduced loss of capacity from cycle to cycle. Moreover, in comparison with a powder-based cathode, a fiber-based cathode is expected to exhibit significantly greater ionic and electronic conduction along the axes of the fibers. Results of preliminary charge/discharge-cycling tests suggest that energy densities of LiCoO2- and LiNiO2-fiber cathodes are approximately double those of the corresponding powder-based cathodes.

Ion dynamics in a new class of materials: nanoglassy lithium alumosilicates

NASA Astrophysics Data System (ADS)

Stanje, B.; Bottke, P.; Breuer, S.; Hanzu, I.; Heitjans, P.; Wilkening, M.

2018-03-01

In many cases nanocrystalline materials, prepared through high-energy ball milling, reveal enhanced ion dynamics when compared to the situation in the coarse-grained analogues. This effect, which has particularly been seen for lithium alumosilicates, has been ascribed to structural disorder, i.e., the introduction of defect sites during mechanical treatment. Much less is, however, known about ion transport in nanostructured amorphous materials, e.g., nanoglassy compounds, which are regarded as a new class of functional materials. Following earlier studies on nanoglassy lithium alumosilicates and borates, here we studied ion dynamics in nanoglassy petalite LiAlSi4O10. While conductivity spectroscopy unequivocally reveals that long-range ion dynamics in nanoglassy LiAlSi4O10 decreases upon milling, local dynamics, sensed by 7Li nuclear magnetic resonance (NMR) spin-lattice relaxation, points to enhanced Li ion mobility compared to the non-treated glass. Most likely, as for nanocrystalline ceramics also for nanoglassy samples a heterogeneous structure, consisting of bulk and interfacial regions, is formed. For LiAlSi4O10 these interfacial regions, characterized by a higher degree of free volume, might act as hosts for spins experiencing fast longitudinal NMR relaxation. Obviously, these regions do not form a through-going network, which would allow the ions to move over long distances as quickly as in the unmilled glass.

Synthesis and Electroluminescent Property of New Orange Iridium Compounds for Flexible White Organic Light Emitting Diodes.

PubMed

Lee, Ho Won; Jeong, Hyunjin; Kim, Young Kwan; Ha, Yunkyoung

2015-10-01

Recently, white organic light-emitting diodes (OLEDs) have aroused considerable attention because they have the potential of next-generation flexible displays and white illuminated applications. White OLED applications are particularly heading to the industry but they have still many problems both materials and manufacturing. Therefore, we proposed that the new iridium compounds of orange emitters could be demonstrated and also applied to flexible white OLEDs for verification of potential. First, we demonstrated the chemical properties of new orange iridium compounds. Secondly, conventional two kinds of white phosphorescent OLEDs were fabricated by following devices; indium-tin oxide coated glass substrate/4,4'-bis[N-(napthyl)-N-phenylamino]biphenyl/N,N'-dicarbazolyl-3,5-benzene doped with blue and new iridium compounds for orange emitting 8 wt%/1,3,5-tris[N-phenylbenzimidazole-2-yl]benzene/lithium quinolate/aluminum. In addition, we fabricated white OLEDs using these emitters to verify the potential on flexible substrate. Therefore, this work could be proposed that white light applications can be applied and could be extended to additional research on flexible applications.

Efficient Electrochemical Synthesis, Antimicrobial and Antiinflammatory Activity of 2–amino-5-substituted- 1,3,4-oxadiazole Derivatives

PubMed Central

Kumar, S.; Srivastava, D. P.

2010-01-01

An efficient electrochemical method for the preparation of 2-amino-5-substituted-1,3,4-oxadiazoles (4a-k) at platinum anode through the electrooxidation of semicarbazone (3a-k) at controlled potential electrolysis has been reported in the present study. The electrolysis was carried out in the acetic acid solvent and lithium perchlorate was used as supporting electrolyte. The products were characterized by IR,1H-NMR,13C-NMR, mass spectra and elemental analysis. The synthesized compounds were screened for their in vitro growth inhibiting activity against different strains of bacteria viz., Klebsilla penumoniae, Escherichia coli, Bassilus subtilis and Streptococcus aureus and antifungal activity against Aspergillus niger and Crysosporium pannical and results have been compared with the standard antibacterial streptomycin and antifungal griseofulvin. Compounds exhibits significant antibacterial activity and antifungal activity. Compounds 4a and g exhibited equal while 4c, d, i and j slightly less antibacterial activity than standard streptomycin. Compounds 4a and g exhibited equal while 4b, c, d, f and i displayed slightly less antifungal activity than standard griseofulvins. PMID:21218056

Hydrogen, lithium, and lithium hydride production

DOEpatents

Brown, Sam W.; Spencer, Larry S.; Phillips, Michael R.; Powell, G. Louis; Campbell, Peggy J.

2017-06-20

A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

Synthesis and electrochemical characterization of Silicon clathrates as anode materials for Lithium ion batteries

NASA Astrophysics Data System (ADS)

Raghavan, Rahul

Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates.

Accelerator-driven boron neutron capture therapy

NASA Astrophysics Data System (ADS)

Edgecock, Rob

2014-05-01

Boron Neutron Capture Therapy is a binary treatment for certain types of cancer. It works by loading the cancerous cells with a boron-10 carrying compound. This isotope has a large cross-section for thermal neutrons, the reaction producing a lithium nucleus and alpha particle that kill the cell in which they are produced. Recent studies of the boron carrier compound indicate that the uptake process works best in particularly aggressive cancers. Most studied is glioblastoma multiforme and a trial using a combination of BNCT and X-ray radiotherapy has shown an increase of nearly a factor of two in mean survival over the state of the art. However, the main technical problem with BNCT remains producing a sufficient flux of neutrons for a reasonable treatment duration in a hospital environment. This paper discusses this issue.

Radiological properties of plastics and TLD materials its application in radiation dosimetry

NASA Astrophysics Data System (ADS)

Jabaseelan Samuel, E. James; Srinivasan, K.; Poopathi, V.

2017-05-01

In the current study, we evaluated the tissue equivalency of nine different commonly used thermoluminescence compounds and six plastic materials over the photon energy range of 15 KeV to 20 MeV. Our result confirmed that the ratio of number of electrons per gram, electron density of the entire TLD compounds and plastic materials to ICRU-44 soft tissue was lesser than unity, except in the case of polypropylene plastics. The effective atomic number ratio of all the plastic materials was also <1 excluding Poly-vinyl-chloride, and for TLD lithium borate material, it was <1 others which showed the deviation with respect to photon energy. Mass attenuation coefficient (µ/ϼ), mass absorption coefficient (µen/ρ) was calculated and the results are discussed in this paper.

Anion-Tunable Properties and Electrochemical Performance of Functionalized Ferrocene Compounds

PubMed Central

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M.; Xu, Wu; Helm, Monte L.; Burton, Sarah D.; Sorensen, Christina M.; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-01-01

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Finally, the electrochemical performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability. PMID:26374254

Anion-tunable properties and electrochemical performance of functionalized ferrocene compounds

DOE PAGES

Cosimbescu, Lelia; Wei, Xiaoliang; Vijayakumar, M.; ...

2015-09-16

We report a series of ionically modified ferrocene compounds for hybrid lithium-organic non-aqueous redox flow batteries, based on the ferrocene/ferrocenium redox couple as the active catholyte material. Tetraalkylammonium ionic moieties were incorporated into the ferrocene structure, in order to enhance the solubility of the otherwise relatively insoluble ferrocene. The effect of various counter anions of the tetraalkylammonium ionized species appended to the ferrocene, such as bis(trifluoromethanesulfonyl)imide, hexafluorophosphate, perchlorate, tetrafluoroborate, and dicyanamide on the solubility of the ferrocene was investigated. The solution chemistry of the ferrocene species was studied, in order to understand the mechanism of solubility enhancement. Lastly, the electrochemicalmore » performance of these ionized ferrocene species was evaluated and shown to have excellent cell efficiency and superior cycling stability.« less

Neutron imaging systems utilizing lithium-containing semiconductor crystals

DOEpatents

Stowe, Ashley C.; Burger, Arnold

2017-04-25

A neutron imaging system, including: a plurality of Li-III-VI.sub.2 semiconductor crystals arranged in an array, wherein III represents a Group III element and VI represents a Group VI element; and electronics operable for detecting and a charge in each of the plurality of crystals in the presence of neutrons and for imaging the neutrons. Each of the crystals is formed by: melting the Group III element; adding the Li to the melted Group III element at a rate that allows the Li and Group III element to react, thereby providing a single phase Li-III compound; and adding the Group VI element to the single phase Li-III compound and heating. Optionally, each of the crystals is also formed by doping with a Group IV element activator.

Nickel-titanium-phosphate cathodes

DOEpatents

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

2008-12-16

Cathode materials having an improved electronic conductivity allowing for faster kinetics in the electrochemical reaction, as well as higher conductivity to meet the power requirements for many consumer applications, especially at low temperatures. The cathode material comprises a compound from the family of compounds where the basic unit is generally represented by Li.sub.xNi.sub.0.5TiOPO.sub.4. The structure of Li.sub.xNi.sub.0.5TiOPO.sub.4 includes corner sharing octahedra [TiO.sub.6] running along the C-axis. The structure is such that nearly three Li atoms are being inserted in Li.sub.xNi.sub.0.5TiOPO.sub.4. A cell in accordance with the principles of the present invention is rechargable and demonstrates a high capacity of lithium intercalation and fast kinetics.

High temperature compounds for turbine vanes

NASA Technical Reports Server (NTRS)

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

1972-01-01

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

Hydrogen, lithium, and lithium hydride production

DOEpatents

Brown, Sam W; Spencer, Larry S; Phillips, Michael R; Powell, G. Louis; Campbell, Peggy J

2014-03-25

A method of producing high purity lithium metal is provided, where gaseous-phase lithium metal is extracted from lithium hydride and condensed to form solid high purity lithium metal. The high purity lithium metal may be hydrided to provide high purity lithium hydride.

designer phase transitions in lithium-based spinels

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

Wouter Montfrooij

When electrons in a metal become correlated with each other, new cooperative behavior can arise. This correlation is magnified when the metal has magnetic ions embedded in it. These atomic magnets try to line up with each other, but in doing so actually create a correlation between the motions of conduction electrons. In turn, these correlated electron motions prevent the magnetic ions from aligning, even at zero Kelvin. When this competition is strongest (at the so-called quantum critical point-QCP) the response of the system can no longer be described using the text book theory for metals. In addition, a rangemore » of new phenomena has been seen to emerge in the vicinity of a QCP, such as heavy-fermion superconductivity, coexistence of magnetism and superconductivity and hyper-scaling. The main goal of our research is to try to unravel the details of the feedback mechanism between electron motion and magnetism that lies at the heart of this new physics. We have chosen lithium-based spinel structures as the most promising family of systems to achieve our goal. Known lithium-based spinels Li{sub x}M{sub 2}O{sub 4} [M=V, Ti and Mn] show a variety of ground states: heavy-fermion, superconducting, or geometrically frustrated local moment systems. Li{sub x}M{sub 2}O{sub 4} should be ideal systems for studying QCPs since their properties can easily be fine-tuned, simply by extracting some Li [which can be done without introducing disorder in the immediate surroundings of the magnetic ions]. The premise of the proposal was that since this Li-extraction can be done both in the metallic as well as in insulating compounds, that we can expand the types of quantum phase transitions that can be studied to beyond transitions in magnetic metals. The project called for developing a better understanding of quantum phase transitions by measuring all aspects of the electronic response of Li{sub x}M{sub 2}O{sub 4} by means of neutron scattering, giving microscopic information about the behavior of the individual magnetic moments and their interactions, as well as by macroscopic measurements. In addition, the aim was to synthesize new lithium-based spinel compounds by using other transition metals that exhibit both 3{sup +} and 4{sup +} valencies. Here we report on the progress we have made during the course of this grant both towards the stated goals and on new avenues that developed as a direct result of the data we collected during this grant.« less

Synthesis, strctural and electrochemical characterizations of lithium- manganese- rich composite cathode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Dapeng

The electrification trend for transportation systems requires alternative cathode materials to LiCoO2 with improved safety, lowered cost and extended cycle life. Lithium- manganese- rich composite cathode materials, which can be presented in a two component notation as xLi2MnO3·(1-x)LiMO 2, (M= Ni, Co or Mn) have superior cost and energy density advantages. These cathode materials have shown success in laboratory scale experiments, but are still facing challenges such as voltage fade, moderate rate capacity and tap density for commercialization. The synthesis of precursors with high packing density and suitable physical properties is critical to achieve high energy density as well as the other acceptable electrochemical performance for the next generation lithium ion batteries. The aim of this study is to correlate the electrochemical properties of materials to their structural, morphological, and physical properties by coordinating the science of synthesis with the science of function, in order to enable the use of these compounds in vehicle technologies. Three different precursors including carbonate, hydroxide and oxalate were synthesized by co-precipitation reactions using continuous stirred tank reactor (CSTR) under various conditions. Research focused on areas such as nucleation and growth mechanisms, synthesis optimizations, and intrinsic limitations of each co-precipitation method. A combination of techniques such as PSA, BET, SEM, EDX FIB, TEM, Raman, FTIR, TGA-DSC, XRD, and ICP-MS, as well as electrochemical test methods such as cycling, CV, EIS and HPPC tests were used in correlation with each other in order to deepen our understanding to these materials. Related topics such as the composite structure formation process during the solid state reaction, lithium and nickel content effects on the cathode properties were also discussed. Additionally, the side reactions between the active materials and electrolyte as a result of the high charge potential were mitigated through a simple wet chemical surface coating method, and the positive effect of the surface coating on the cells' performance was also discussed.

Synaptic potentials recorded by the sucrosegap method from the rabbit superior cervical ganglion

PubMed Central

Kosterlitz, H. W.; Lees, G. M.; Wallis, D. I.

1970-01-01

1. Compound ganglionic potentials evoked by stimulation of the preganglionic nerves to the superior cervical ganglion of the rabbit were recorded by the sucrose-gap method. 2. When the distal part of the ganglion was bathed in flowing isotonic sucrose solution or sodium-deficient solutions, ganglionic action potentials were no longer evoked, only large synaptic potentials. 3. The compound synaptic potential, which remained unaltered for more than 1 h, originated in a population of cells at the interface between the Krebs and sucrose solutions. Hexamethonium reduced the size but did not alter the time course of the synaptic potential. 4. It is suggested that a higher concentration of sodium ions is required for the generation of ganglionic action potentials than for either conduction in the postganglionic axons or production of synaptic potentials. 5. When lithium replaced sodium in the solution bathing the distal part of the ganglion, the synaptic potential was greatly reduced in amplitude. Impulse propagation in the postganglionic axons was only slightly impaired when lithium replaced sodium in the solution bathing the axons. 6. A quantitative assessment of the potency of the ganglion-blocking drugs nicotine, pentolinium, hexamethonium and pempidine was made by measuring the depression of the synaptic potentials produced by bathing the distal part of the ganglion in flowing isotonic sucrose solution. The concentrations which produced a 50% depression were 8·1 μM nicotine, 26·5 μM pentolinium, 111 μM hexamethonium and 22·2 μM pempidine. PMID:5492898

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries

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

Luo, Chao; Xu, Gui-Liang; Ji, Xiao

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAhg -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAhg -1 can be retained for 2000 cycles, demonstratingmore » excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na +. The reversible redox chemistry between azo compound and Na ions offer opportunities for developing longcycle-life and high-rate SSIBs.« less

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries

DOE PAGES

Luo, Chao; Xu, Gui-Liang; Ji, Xiao; ...

2018-01-29

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAhg -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAhg -1 can be retained for 2000 cycles, demonstratingmore » excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na +. The reversible redox chemistry between azo compound and Na ions offer opportunities for developing longcycle-life and high-rate SSIBs.« less

Non-aqueous electrolyte for lithium-ion battery

DOEpatents

Amine, Khalil; Zhang, Lu; Zhang, Zhengcheng

2016-01-26

A substantially non-aqueous electrolyte solution includes an alkali metal salt, a polar aprotic solvent, and an organophosphorus compound of Formula IA, IB, or IC: ##STR00001## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkoxy, alkenoxy, alkynoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, siloxyl, silyl, or organophosphatyl; R.sup.5 and R.sup.6 are each independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; R.sup.7 is ##STR00002## and R.sup.8, R.sup.9 and R.sup.10 are each independently alkyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; provided that if the organophosphorus compound is of Formula IB, then at least one of R.sup.5, and R.sup.6 are other than hydrogen, alkyl, or alkenyl; and if the organophosphorus compound is of Formula IC, then the electrolyte solution does not include 4-methylene-1,3-dioxolan-2-one or 4,5-dimethylene-1,3-dioxolan-2-one.

77 FR 21714 - Hazardous Materials: Transportation of Lithium Batteries

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-11

... and configurations of lithium batteries: 1. Lithium ion batteries (PI 965). 2. Lithium ion batteries packed with equipment (PI 966). 3. Lithium ion batteries contained in equipment (PI 967). 4. Lithium... requirements including package weight limits (10 kg for lithium ion cells and batteries and 2.5 kg for lithium...

Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method

DOEpatents

Bates, John B.

1994-01-01

A battery structure including a cathode, a lithium metal anode and an electrolyte disposed between the lithium anode and the cathode utilizes a thin-film layer of lithium phosphorus oxynitride overlying so as to coat the lithium anode and thereby separate the lithium anode from the electrolyte. If desired, a preliminary layer of lithium nitride may be coated upon the lithium anode before the lithium phosphorous oxynitride is, in turn, coated upon the lithium anode so that the separation of the anode and the electrolyte is further enhanced. By coating the lithium anode with this material lay-up, the life of the battery is lengthened and the performance of the battery is enhanced.

Alkali metal complexes of sterically demanding amino-functionalized secondary phosphanide ligands.

PubMed

Izod, Keith; Stewart, John C; Clegg, William; Harrington, Ross W

2007-01-14

The reaction between {(Me(3)Si)(2)CH}PCl(2) (4) and one equivalent of either [C(6)H(4)-2-NMe(2)]Li or [2-C(5)H(4)N]ZnCl, followed by in situ reduction with LiAlH(4) gives the secondary phosphanes {(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))PH (5) and {(Me(3)Si)(2)CH}(2-C(5)H(4)N)PH (6) in good yields as colourless oils. Metalation of 5 with Bu(n)Li in THF gives the lithium phosphanide [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]Li(THF)(2)] (7), which undergoes metathesis with either NaOBu(t) or KOBu(t) to give the heavier alkali metal derivatives [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]Na(tmeda)] (8) and [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]K(pmdeta)] (9) after recrystallization in the presence of the corresponding amine co-ligand [tmeda = N,N,N',N'-tetramethylethylenediamine, pmdeta = N,N,N',N'',N''-pentamethyldiethylenetriamine]. The pyridyl-functionalized phosphane 6 undergoes deprotonation on treatment with Bu(n)Li to give a red oil corresponding to the lithium compound [{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]Li (10) which could not be crystallized. Treatment of this oil with NaOBu(t) gives the sodium derivative [{[{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]Na}(2) x (Et(2)O)](2) (11), whilst treatment of with KOBu(t), followed by recrystallization in the presence of pmdeta gives the complex [[{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]K(pmdeta)](2) (12). Compounds 5-12 have been characterised by (1)H, (13)C{(1)H} and (31)P{(1)H} NMR spectroscopy and elemental analyses; compounds 7-9, and 12 have additionally been characterised by X-ray crystallography. Compounds 7-9 crystallize as discrete monomers, whereas 11 crystallizes as an unusual dimer of dimers and 12 crystallizes as a dimer with bridging pyridyl-phosphanide ligands.

A stable organic-inorganic hybrid layer protected lithium metal anode for long-cycle lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Zhu, Jinhui; Yang, Jun; Zhou, Jingjing; Zhang, Tao; Li, Lei; Wang, Jiulin; Nuli, Yanna

2017-10-01

A stable organic-inorganic hybrid layer (OIHL) is direct fabricated on lithium metal surface by the interfacial reaction of lithium metal foil with 1-chlorodecane and oxygen/carbon dioxide mixed gas. This favorable OIHL is approximately 30 μm thick and consists of lithium alkyl carbonate and lithium chloride. The lithium-oxygen batteries with OIHL protected lithium metal anode exhibit longer cycle life (340 cycles) than those with bare lithium metal anode (50 cycles). This desirable performance can be ascribed to the robust OIHL which prevents the growth of lithium dendrites and the corrosion of lithium metal.

Li1.2Mn0.6Ni0.1Co0.1O2 microspheres constructed by hierarchically arranged nanoparticles as lithium battery cathode with enhanced electrochemical performance

NASA Astrophysics Data System (ADS)

Remith, P.; Kalaiselvi, N.

2014-11-01

Novel lithium-rich layered Li1.2Mn0.6Ni0.1Co0.1O2 microspheres containing hierarchically arranged and interconnected nanostructures have been synthesized by a combination of template-free co-precipitation and solid-state methods. The in situ formed γ-MnO2 spherical template upon co-precipitation gets sacrificed during the course of solid-state fusion of cobalt, nickel and lithium precursors to produce the title compound in the form of microspheres constructed by nanoparticles as building blocks. Porous and hollow microspheres of Li1.2Mn0.6Ni0.1Co0.1O2 are formed out of the spontaneous aggregation of nanoparticles, obtained from the custom-designed synthesis protocol. The growth mechanism of Li1.2Mn0.6Ni0.1Co0.1O2 spheres could be understood in terms of the Kirkendall effect and Ostwald ripening. The nanocrystalline Li1.2Mn0.6Ni0.1Co0.1O2 compound is obtained as a solid solution consisting of rhombohedral R3&cmb.macr;m and monoclinic C2/m group symmetries, as evidenced by XRD, Raman spectra and HRTEM equipped with FFT and STEM. The currently synthesized Li1.2Mn0.6Ni0.1Co0.1O2 cathode exhibits an appreciable discharge capacity of 242 mA h g-1 at a current density of 50 mA g-1, due to the synergistic effect of the capacity obtained from the rhombohedral and monoclinic phases.Novel lithium-rich layered Li1.2Mn0.6Ni0.1Co0.1O2 microspheres containing hierarchically arranged and interconnected nanostructures have been synthesized by a combination of template-free co-precipitation and solid-state methods. The in situ formed γ-MnO2 spherical template upon co-precipitation gets sacrificed during the course of solid-state fusion of cobalt, nickel and lithium precursors to produce the title compound in the form of microspheres constructed by nanoparticles as building blocks. Porous and hollow microspheres of Li1.2Mn0.6Ni0.1Co0.1O2 are formed out of the spontaneous aggregation of nanoparticles, obtained from the custom-designed synthesis protocol. The growth mechanism of Li1.2Mn0.6Ni0.1Co0.1O2 spheres could be understood in terms of the Kirkendall effect and Ostwald ripening. The nanocrystalline Li1.2Mn0.6Ni0.1Co0.1O2 compound is obtained as a solid solution consisting of rhombohedral R3&cmb.macr;m and monoclinic C2/m group symmetries, as evidenced by XRD, Raman spectra and HRTEM equipped with FFT and STEM. The currently synthesized Li1.2Mn0.6Ni0.1Co0.1O2 cathode exhibits an appreciable discharge capacity of 242 mA h g-1 at a current density of 50 mA g-1, due to the synergistic effect of the capacity obtained from the rhombohedral and monoclinic phases. Electronic supplementary information (ESI) available: Fig. S1 represents the STEM elemental mapping of pristine Li1.2Mn0.6Ni0.1Co0.1O2. Fig. S2 is the EDX spectrum obtained from HRTEM and Fig. S3 is the SAED pattern. Fig. S4 shows the room temperature conductivity plot and Fig. S5 shows the comparison of the discharge capacity values of LiMn1/3Ni1/3Co1/3O2 and Li1.2Mn0.6Ni0.1Co0.1O2 cathodes and Table 1 shows the d spacing values corresponding to different space group symmetries, derived from XRD and TEM studies. See DOI: 10.1039/c4nr04314f

Multinuclear NMR Study of the Solid Electrolyte Interface Formed in Lithium Metal Batteries

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

Wan, Chuan; Xu, Suochang; Hu, Mary Y.

The composition of the solid electrolyte interphase (SEI) layers associated with a high performance Cu|Li cell using lithium bis(fluorosulfonyi)imide (LiFSI) in 1,2-dimethoxyethane (DME) as electrolyte is determined by a multinuclear (6Li, 19F, 13C and 1H) solid-state MAS NMR study at high magnetic field (850 MHz). This cell can be cycled at high rates (4 mA•cm-2) for more than 1000 cycles with no increase in the cell impedance at high Columbic efficiency (average of 98.4%) in a highly concentrated LiFSI-DME electrolyte (4 M). LiFSI, LiF, Li2O2 (and/or CH3OLi), LiOH, Li2S and Li2O are observed in the SEI and validated by comparingmore » with the spectra acquired on standard compounds and literature reports. To gain further insight into the role of the solute and its concentration dependence on the formation of SEIs while keeping the solvent of DME unchanged, the SEIs from different concentrations of LiFSI-DME and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-DME electrolyte are also investigated. It is found that LiF, a lithiated compound with superior mechanical strength and good Li+ ionic conductivity, is observed in the concentrated 4.0 M LiFSI-DME and the 3.0 M LiTFSI-DME systems but not in the diluted 1.0 M LiFSI-DME system. Li2O exists in both low and high concentration of LiFSI-DME while no Li2O is observed in the LiTFSI system. Furthermore, the dead metallic Li is reduced in the 4 M LiFSI-DME system compared with that in the 1 M LiFSI-DME system. Quantitative 6Li MAS results indicate that the SEI associated with the 4 M LiFSI-DEME is denser or thicker than that of the 1 M LiFSI-DME and the 3 M LiTFSI-DME systems. These findings are likely the reasons for explaining the high electrochemical performance associated with the high concentration LiFSI-DME system.« less

Advanced Micro/Nanostructures for Lithium Metal Anodes

PubMed Central

Zhang, Rui; Li, Nian‐Wu; Cheng, Xin‐Bing; Yin, Ya‐Xia

2017-01-01

Owning to their very high theoretical capacity, lithium metal anodes are expected to fuel the extensive practical applications in portable electronics and electric vehicles. However, unstable solid electrolyte interphase and lithium dendrite growth during lithium plating/stripping induce poor safety, low Coulombic efficiency, and short span life of lithium metal batteries. Lately, varies of micro/nanostructured lithium metal anodes are proposed to address these issues in lithium metal batteries. With the unique surface, pore, and connecting structures of different nanomaterials, lithium plating/stripping processes have been regulated. Thus the electrochemical properties and lithium morphologies have been significantly improved. These micro/nanostructured lithium metal anodes shed new light on the future applications for lithium metal batteries. PMID:28331792

76 FR 53056 - Outbound International Mailings of Lithium Batteries

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-25

... or lithium-ion batteries in accordance with Packing Instruction 967, Section II, or Packing... Secondary Lithium-ion (Rechargeable) Cells and Batteries. Small consumer-type lithium-ion cells and... shipment may contain a maximum of four lithium-ion cells or two lithium-ion batteries. c. The lithium...

LiBSi2: a tetrahedral semiconductor framework from boron and silicon atoms bearing lithium atoms in the channels.

PubMed

Zeilinger, Michael; van Wüllen, Leo; Benson, Daryn; Kranak, Verina F; Konar, Sumit; Fässler, Thomas F; Häussermann, Ulrich

2013-06-03

Silicon swallows up boron: The novel open tetrahedral framework structure (OTF) of the Zintl phase LiBSi2 was made by applying high pressure to a mixture of LiB and elemental silicon. The compound represents a new topology in the B-Si net (called tum), which hosts Li atoms in the channels (see picture). LiBSi2 is the first example where B and Si atoms form an ordered common framework structure with B engaged exclusively in heteronuclear B-Si contacts.

Thermal neutron scintillators using unenriched boron nitride and zinc sulfide

NASA Astrophysics Data System (ADS)

McMillan, J. E.; Cole, A. J.; Kirby, A.; Marsden, E.

2015-06-01

Thermal neutron detectors based on powdered zinc sulfide intimately mixed with a neutron capture compound have a history as long as scintillation technique itself. We show that using unenriched boron nitride powder, rather than the more commonly used enriched lithium fluoride, results in detection screens which produce less light but which are very considerably cheaper. Methods of fabricating large areas of this material are presented. The screens are intended for the production of large area low cost neutron detectors as a replacement for helium-3 proportional tubes.

Effects of land use on water quality of the Fountain Creek alluvial aquifer, east-central Colorado

USGS Publications Warehouse

Chafin, Daniel T.

1996-01-01

Water-quality data were collected from the Fountain Creek alluvial aquifer in 1988 and 1989 as part of the Toxic-Waste Ground-Water Contamination Program. These data indicate that dissolved solids, most major ions, fluoride, ammonium, boron, lithium, selenium, and strontium were more concentrated in the agricultural land-use area than in the upgradient urban land-use area. Nitrate and phosphate had significantly larger concentrations, and volatile organic compounds had significantly greater detection frequencies in the urban land-use area.

Research, Development and Fabrication of Lithium Solar Cells, Part 2

NASA Technical Reports Server (NTRS)

Iles, P. A.

1972-01-01

The development and fabrication of lithium solar cells are discussed. Several single-step, lithium diffusion schedules using lower temperatures and times are described. A comparison was made using evaporated lithium metal as the lithium source, and greatly improved consistency in lithium concentrations was obtained. It was possible to combine all processing steps to obtain lithium doped cells of high output which also contained adequate lithium to ensure good recoverability.

Secondary electron emission from lithium and lithium compounds

DOE PAGES

Capece, A. M.; Patino, M. I.; Raitses, Y.; ...

2016-07-06

In this work, measurements of electron-induced secondary electron emission ( SEE) yields of lithium as a function of composition are presented. The results are particularly relevant for magnetic fusion devices such as tokamaks, field-reversed configurations, and stellarators that consider Li as a plasma-facing material for improved plasma confinement. SEE can reduce the sheath potential at the wall and cool electrons at the plasma edge, resulting in large power losses. These effects become significant as the SEE coefficient, γ e, approaches one, making it imperative to maintain a low yield surface. This work demonstrates that the yield from Li strongly dependsmore » on chemical composition and substantially increases after exposure to oxygen and water vapor. The total yield was measured using a retarding field analyzer in ultrahigh vacuum for primary electron energies of 20-600 eV. The effect of Li composition was determined by introducing controlled amounts of O 2 and H 2O vapor while monitoring film composition with Auger electron spectroscopy and temperature programmed desorption. The results show that the energy at which γ e = 1 decreases with oxygen content and is 145 eV for a Li film that is 17% oxidized and drops to less than 25 eV for a fully oxidized film. This work has important implications for laboratory plasmas operating under realistic vacuum conditions in which oxidation significantly alters the electron emission properties of Li walls. Published by AIP Publishing.« less

First-principles study of lithium ion migration in lithium transition metal oxides with spinel structure.

PubMed

Nakayama, Masanobu; Kaneko, Mayumi; Wakihara, Masataka

2012-10-28

The migration of lithium (Li) ions in electrode materials is an important factor affecting the rate performance of rechargeable Li ion batteries. We have examined Li migration in spinels LiMn(2)O(4), LiCo(2)O(4), and LiCo(1/16)Mn(15/16)O(4) by means of first-principles calculations based on density functional theory (DFT). The results showed that the trajectory of the Li jump was straight between the two adjacent Li ions for all of the three spinel compounds. However, there were significant differences in the energy profiles and the Li jump path for LiMn(2)O(4) and LiCo(2)O(4). For LiMn(2)O(4) the highest energy barrier was in the middle of the two tetrahedral sites, or in the octahedral vacancy (16c). For LiCo(2)O(4) the lowest energy was around the octahedral 16c site and the energy barrier was located at the bottleneck sites. The difference in the energy profile for LiCo(2)O(4) stemmed from the charge disproportion of Co(3.5+) to Co(3+)/Co(4+) caused by a Li vacancy forming and jumping, which was not observed for LiMn(2)O(4). Charge disproportion successfully accounted for the faster Li migration mechanism observed in LiCo(1/16)Mn(15/16)O(4). Our computational results demonstrate the importance of the effect of charge distribution on the ion jump.

Secondary electron emission from lithium and lithium compounds

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

Capece, A. M., E-mail: capecea@tcnj.edu; Department of Physics, The College of New Jersey, Ewing, New Jersey 08628; Patino, M. I.

2016-07-04

In this work, measurements of electron-induced secondary electron emission (SEE) yields of lithium as a function of composition are presented. The results are particularly relevant for magnetic fusion devices such as tokamaks, field-reversed configurations, and stellarators that consider Li as a plasma-facing material for improved plasma confinement. SEE can reduce the sheath potential at the wall and cool electrons at the plasma edge, resulting in large power losses. These effects become significant as the SEE coefficient, γ{sub e}, approaches one, making it imperative to maintain a low yield surface. This work demonstrates that the yield from Li strongly depends onmore » chemical composition and substantially increases after exposure to oxygen and water vapor. The total yield was measured using a retarding field analyzer in ultrahigh vacuum for primary electron energies of 20–600 eV. The effect of Li composition was determined by introducing controlled amounts of O{sub 2} and H{sub 2}O vapor while monitoring film composition with Auger electron spectroscopy and temperature programmed desorption. The results show that the energy at which γ{sub e} = 1 decreases with oxygen content and is 145 eV for a Li film that is 17% oxidized and drops to less than 25 eV for a fully oxidized film. This work has important implications for laboratory plasmas operating under realistic vacuum conditions in which oxidation significantly alters the electron emission properties of Li walls.« less

Controllable synthesis of SnO2@carbon hollow sphere based on bi-functional metallo-organic molecule for high-performance anode in Li-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Haiyan; Li, Liuqing; Li, Zhaopeng; Zhong, Weihao; Liao, Haiyang; Li, Zhenghui

2018-06-01

Constructing hollow structure and nano-sized SnO2 particles are two normal strategies to improve lithium storage performance of SnO2-based electrode. But it is still challengeable to fabricate ultrasmall SnO2 embedded in carbon hollow sphere in a controllable way. Herein, we have synthesized a kind of SnO2@carbon hollow sphere via a confined Friedel-Crafts crosslinking of a novel metal-organic compound (triphenyltin chloride, named Sn-Ph) on the surface of SiO2 template. The as-prepared SnO2@carbon hollow sphere has 10 nm-sized SnO2 particles embedded in amorphous carbon wall. Furthermore, 100, 200 and 400 nm-sized SnO2@carbon hollow spheres can be obtained by regulating the size of SiO2 template. When they are applied in lithium-ion batteries, the carbon structure can act as barriers to protect SnO2 particles from pulverization, and hollow core stores electrolyte and very small SnO2 particles of 10 nm shorten the diffusion distance of lithium ions. Thus, SnO2@carbon hollow sphere presents superior electrochemical performance. The first discharge and charge capacities reach 1378.5 and 507.3 mAh g-1 respectively, and 100 cycles later, its capacity remains 501.2 mAh g-1, indicating a capacity retention of 98.8% (C100th/C2nd).

A search map for organic additives and solvents applicable in high-voltage rechargeable batteries.

PubMed

Park, Min Sik; Park, Insun; Kang, Yoon-Sok; Im, Dongmin; Doo, Seok-Gwang

2016-09-29

Chemical databases store information such as molecular formulas, chemical structures, and the physical and chemical properties of compounds. Although the massive databases of organic compounds exist, the search of target materials is constrained by a lack of physical and chemical properties necessary for specific applications. With increasing interest in the development of energy storage systems such as high-voltage rechargeable batteries, it is critical to find new electrolytes efficiently. Here we build a search map to screen organic additives and solvents with novel core and functional groups, and thus establish a database of electrolytes to identify the most promising electrolyte for high-voltage rechargeable batteries. This search map is generated from MAssive Molecular Map BUilder (MAMMBU) by combining a high-throughput quantum chemical simulation with an artificial neural network algorithm. MAMMBU is designed for predicting the oxidation and reduction potentials of organic compounds existing in the massive organic compound database, PubChem. We develop a search map composed of ∼1 000 000 redox potentials and elucidate the quantitative relationship between the redox potentials and functional groups. Finally, we screen a quinoxaline compound for an anode additive and apply it to electrolytes and improve the capacity retention from 64.3% to 80.8% near 200 cycles for a lithium ion battery in experiments.

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

Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai

The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturatedmore » moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.« less

Biological activity of N(4)-boronated derivatives of 2'-deoxycytidine, potential agents for boron-neutron capture therapy.

PubMed

Nizioł, Joanna; Uram, Łukasz; Szuster, Magdalena; Sekuła, Justyna; Ruman, Tomasz

2015-10-01

Boron-neutron capture therapy (BNCT) is a binary anticancer therapy that requires boron compound for nuclear reaction during which high energy alpha particles and lithium nuclei are formed. Unnatural, boron-containing nucleoside with hydrophobic pinacol moiety was investigated as a potential BNCT boron delivery agent. Biological properties of this compound are presented for the first time and prove that boron nucleoside has low cytotoxicity and that observed apoptotic effects suggest alteration of important functions of cancer cells. Mass spectrometry analysis of DNA from cancer cells proved that boron nucleoside is inserted into nucleic acids as a functional nucleotide derivative. NMR studies present very high degree of similarity of natural dG-dC base pair with dG-boron nucleoside system. Copyright © 2015 Elsevier Ltd. All rights reserved.

21 CFR 862.3560 - Lithium test system.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Lithium test system. 862.3560 Section 862.3560....3560 Lithium test system. (a) Identification. A lithium test system is a device intended to measure lithium (from the drug lithium carbonate) in serum or plasma. Measurements of lithium are used to assure...

21 CFR 862.3560 - Lithium test system.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Lithium test system. 862.3560 Section 862.3560....3560 Lithium test system. (a) Identification. A lithium test system is a device intended to measure lithium (from the drug lithium carbonate) in serum or plasma. Measurements of lithium are used to assure...

21 CFR 862.3560 - Lithium test system.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Lithium test system. 862.3560 Section 862.3560....3560 Lithium test system. (a) Identification. A lithium test system is a device intended to measure lithium (from the drug lithium carbonate) in serum or plasma. Measurements of lithium are used to assure...

21 CFR 862.3560 - Lithium test system.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Lithium test system. 862.3560 Section 862.3560....3560 Lithium test system. (a) Identification. A lithium test system is a device intended to measure lithium (from the drug lithium carbonate) in serum or plasma. Measurements of lithium are used to assure...

21 CFR 862.3560 - Lithium test system.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Lithium test system. 862.3560 Section 862.3560....3560 Lithium test system. (a) Identification. A lithium test system is a device intended to measure lithium (from the drug lithium carbonate) in serum or plasma. Measurements of lithium are used to assure...

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

PubMed

Zu, Chenxi; Manthiram, Arumugam

2014-08-07

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

Lanthanum Nitrate As Electrolyte Additive To Stabilize the Surface Morphology of Lithium Anode for Lithium-Sulfur Battery.

PubMed

Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

2016-03-01

Lithium-sulfur (Li-S) battery is regarded as one of the most promising candidates beyond conventional lithium ion batteries. However, the instability of the metallic lithium anode during lithium electrochemical dissolution/deposition is still a major barrier for the practical application of Li-S battery. In this work, lanthanum nitrate, as electrolyte additive, is introduced into Li-S battery to stabilize the surface of lithium anode. By introducing lanthanum nitrate into electrolyte, a composite passivation film of lanthanum/lithium sulfides can be formed on metallic lithium anode, which is beneficial to decrease the reducibility of metallic lithium and slow down the electrochemical dissolution/deposition reaction on lithium anode for stabilizing the surface morphology of metallic Li anode in lithium-sulfur battery. Meanwhile, the cycle stability of the fabricated Li-S cell is improved by introducing lanthanum nitrate into electrolyte. Apparently, lanthanum nitrate is an effective additive for the protection of lithium anode and the cycling stability of Li-S battery.

Method of recycling lithium borate to lithium borohydride through diborane

DOEpatents

Filby, Evan E.

1976-01-01

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

Development of lithium powder based anode with conductive carbon materials for lithium batteries

NASA Astrophysics Data System (ADS)

Park, Man Su

Current lithium ion battery with a graphite anode shows stable cycle performance and safety. However, the lithium ion battery still has the limitation of having a low energy density caused by the application of lithium intercalated cathode and anode with low energy density. The combination of high capacity non-lithiated cathode such as sulfur and carbon and lithium metal anode has been researched for a long time to maximize battery's energy density. However, this cell design also has a lot of technical challenges to be solved. Among the challenges, lithium anode's problem related to lithium dendrite growth causing internal short and low cycling efficiency is very serious. Thus, extensive research on lithium metal anode has been performed to solve the lithium dendrite problem and a major part of the research has been focused on the control of the interface between lithium and electrolyte. However, research on lithium anode design itself has not been much conducted. In this research, innovative lithium anode design for less dendrite growth and higher cycling efficiency was suggested. Literature review for the lithium dendrite growth mechanism was conducted in Chapter 2 to develop electrode design concept and the importance of the current density on lithium dendrite growth was also found in the literatures. The preliminary test was conducted to verify the developed electrode concept by using lithium powder based anode (LIP) with conductive carbon materials and the results showed that lithium dendrite growth could be suppressed in this electrode design due to its increased electrochemical surface area and lithium deposition sites during lithium deposition. The electrode design suggested in Chapter 2 was extensively studied in Chapter 3 in terms of lithium dendrite growth morphology, lithium cycling efficiency and full cell cycling performance. This electrode concept was further developed to maximize the electrode's performance and safety in Chapter 4. In this new electrode design, electrically isolated super-p carbon agglomerates in the electrode were effectively reduced by adding conductive fillers such as graphite and further improvement in cycling performance and safety was also verified. The lithium powder based anode with conductive carbon materials is very useful concept as an alternative anode design instead of pure lithium metal anode for high energy density lithium batteries such as lithium-sulfur and lithium-air. As shown in Chapter 5, this electrode concept can be further developed and optimized through the application of new carbon materials and structure.

Method of recycling lithium borate to lithium borohydride through methyl borate

DOEpatents

Filby, Evan E.

1977-01-01

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

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.

Sodium titanate nanotubes as negative electrode materials for sodium-ion capacitors.

PubMed

Yin, Jiao; Qi, Li; Wang, Hongyu

2012-05-01

The lithium-based energy storage technology is currently being considered for electric automotive industry and even electric grid storage. However, the hungry demand for vast energy sources in the modern society will conflict with the shortage of lithium resources on the earth. The first alternative choice may be sodium-related materials. Herein, we propose an electric energy storage system (sodium-ion capacitor) based on porous carbon and sodium titanate nanotubes (Na-TNT, Na(+)-insertion compounds) as positive and negative electrode materials, respectively, in conjunction with Na(+)-containing non-aqueous electrolytes. As a low-voltage (0.1-2 V) sodium insertion nanomaterial, Na-TNT was synthesized via a simple hydrothermal reaction. Compared with bulk sodium titanate, the predominance of Na-TNT is the excellent rate performance, which exactly caters to the need for electrochemical capacitors. The sodium-ion capacitors exhibited desirable energy density and power density (34 Wh kg(-1), 889 W kg(-1)). Furthermore, the sodium-ion capacitors had long cycling life (1000 cycles) and high coulombic efficiency (≈ 98 % after the second cycle). More importantly, the conception of sodium-ion capacitor has been put forward.

Ternary metal fluorides as high-energy cathodes with low cycling hysteresis

DOE PAGES

Wang, Feng; Kim, Sung -Wook; Seo, Dong -Hwa; ...

2015-03-26

In this study, transition metal fluorides are an appealing alternative to conventional intercalation compounds for use as cathodes in next-generation lithium batteries due to their extremely high capacity (3–4 times greater than the current state-of-the-art). However, issues related to reversibility, energy efficiency and kinetics prevent their practical application. Here we report on the synthesis, structural and electrochemical properties of ternary metal fluorides (M 1 yM 2 1-yF x: M 1, M 2 = Fe, Cu), which may overcome these issues. By substituting Cu into the Fe lattice, forming the solid–solution Cu yFe 1-yF 2, reversible Cu and Fe redox reactionsmore » are achieved with surprisingly small hysteresis (<150 mV). This finding indicates that cation substitution may provide a new avenue for tailoring key electrochemical properties of conversion electrodes. In conclusion, although the reversible capacity of Cu conversion fades rapidly, likely due to Cu + dissolution, the low hysteresis and high energy suggest that a Cu-based fluoride cathode remains an intriguing candidate for rechargeable lithium batteries.« less

A high-conduction Ge substituted Li3AsS4 solid electrolyte with exceptional low activation energy

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

Sahu, Gayatri; Rangasamy, Ezhiylmurugan; Li, Juchuan

2014-04-16

In lithium-ion conducting solid electrolytes the potential to enable high-energy-density secondary batteries and offer distinctive safety features as an advantage over traditional liquid electrolytes is shown. Achieving the combination of high ionic conductivity, low activation energy, and outstanding electrochemical stability in crystalline solid electrolytes is a challenge for the synthesis of novel solid electrolytes. We report an exceptionally low activation energy (Ea) and high room temperature superionic conductivity via facile aliovalent substitution of Li 3AsS 4 by Ge, which increased the conductivity by two orders of magnitude as compared to the parent compound. The composition Li 3.334Ge 0.334As 0.666S 4more » has a high ionic conductivity of 1.12 mScm -1 at 27°C. Local Li + hopping in this material is accompanied by distinctive low activation energy Ea of 0.17 eV being the lowest of Li + solid conductors. Finally, our study demonstrates the efficacy of surface passivation of solid electrolyte to achieve compatibility with metallic lithium electrodes.« less

Theoretical evaluation of high-energy lithium metal phosphate cathode materials in Li-ion batteries

NASA Astrophysics Data System (ADS)

Howard, Wilmont F.; Spotnitz, Robert M.

Lithium metal phosphates (olivines) are emerging as long-lived, safe cathode materials in Li-ion batteries. Nano-LiFePO 4 already appears in high-power applications, and LiMnPO 4 development is underway. Current and emerging Fe- and Mn-based intercalants, however, are low-energy producers compared to Ni and Co compounds. LiNiPO 4, a high voltage olivine, has the potential for superior energy output (>10.7 Wh in 18650 batteries), compared with commercial Li(Co,Ni)O 2 derivatives (up to 9.9 Wh). Speculative Co and Ni olivine cathode materials charged to above 4.5 V will require significant advances in electrolyte compositions and nanotechnology before commercialization. The major drivers toward 5 V battery chemistries are the inherent abuse tolerance of phosphates and the economic benefit of LiNiPO 4: it can produce 34% greater energy per dollar of cell material cost than LiAl 0.05Co 0.15Ni 0.8O 2, today's "standard" cathode intercalant in Li-ion batteries.

New-concept Batteries Based on Aqueous Li+/Na+ Mixed-ion Electrolytes

PubMed Central

Chen, Liang; Gu, Qingwen; Zhou, Xufeng; Lee, Saixi; Xia, Yonggao; Liu, Zhaoping

2013-01-01

Rechargeable batteries made from low-cost and abundant materials operating in safe aqueous electrolytes are attractive for large-scale energy storage. Sodium-ion battery is considered as a potential alternative of current lithium-ion battery. As sodium-intercalation compounds suitable for aqueous batteries are limited, we adopt a novel concept of Li+/Na+ mixed-ion electrolytes to create two batteries (LiMn2O4/Na0.22MnO2 and Na0.44MnO2/TiP2O7), which relies on two electrochemical processes. One involves Li+ insertion/extraction reaction, and the other mainly relates to Na+ extraction/insertion reaction. Two batteries exhibit specific energy of 17 Wh kg−1 and 25 Wh kg−1 based on the total weight of active electrode materials, respectively. As well, aqueous LiMn2O4/Na0.22MnO2 battery is capable of separating Li+ and Na+ due to its specific mechanism unlike the traditional “rocking-chair” lithium-ion batteries. Hence, the Li+/Na+ mixed-ion batteries offer promising applications in energy storage and Li+/Na+ separation. PMID:23736113

Amorphisation and recrystallisation study of lithium intercalation into TiO2 nano-architecture.

NASA Astrophysics Data System (ADS)

Matshaba, M. G.; Sayle, D. C.; Sayle, T. X. T.; Ngoepe, P. E.

2017-02-01

Titanium dioxide is playing an increasingly significant role in easing environmental and energy concerns. Its rich variety of polymorphic crystal structures has facilitated a wide range of applications such as photo-catalysis, photo-splitting of water, photoelectrochromic devices, insulators in metal oxide, semiconductors devices, dye sensitized solar cells (DSSCs) (energy conversions), rechargeable lithium batteries (electrochemical storage). The complex structural aspects in nano TiO2, are elucidated by microscopic visualization and quantification of the microstructure for electrode materials, since cell performance and various aging mechanisms depend strongly on the appearance and changes in the microstructure. Recent studies on MnO2 have demonstrated that amorphisation and recrystallisation simulation method can adequately generate various nanostructures, for Li-ion battery compounds. The method was also previously employed to produce nano-TiO2. In the current study, the approach is used to study lithiated nanoporous structure for TiO2 which have been extensively studied experimentally, as mentioned above. Molecular graphic images showing microstructural features, including voids and channels have accommodated lithium’s during lithiation and delithiation. Preliminary lithiation of TiO2 will be considered.

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.

Hindered Glymes for Graphite-Compatible Electrolytes.

PubMed

Shanmukaraj, Devaraj; Grugeon, Sylvie; Laruelle, Stephane; Armand, Michel

2015-08-24

Organic carbonate mixtures are used almost exclusively as lithium battery electrolyte solvents. The linear compounds (dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate) act mainly as thinner for the more viscous and high-melting ethylene carbonate but are the least stable component and have low flash points; these are serious handicaps for lifetime and safety. Polyethers (glymes) are useful co-solvents, but all formerly known representatives solvate Li(+) strongly enough to co-intercalate in the graphite negative electrode and exfoliate it. We have put forward a new electrolyte composition comprising a polyether to which a bulky tert-butyl group is attached ("hindered glyme"), thus completely preventing co-intercalation while maintaining good conductivity. This alkyl-carbonate-free electrolyte shows remarkable cycle efficiency of the graphite electrode, not only at room temperature, but also at 50 and 70 °C in the presence of lithium bis(fluorosulfonimide). The two-ethylene-bridge hindered glyme has a high boiling point and a flash point of 80 °C, a considerable advantage for safety. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

APPARATUS FOR THE PRODUCTION OF LITHIUM METAL

DOEpatents

Baker, P.S.; Duncan, F.R.; Greene, H.B.

1961-08-22

Methods and apparatus for the production of high-purity lithium from lithium halides are described. The apparatus is provided for continuously contacting a molten lithium halide with molten barium, thereby forming lithium metal and a barium halide, establishing separate layers of these reaction products and unreacted barium and lithium halide, and continuously withdrawing lithium and barium halide from the reaction zone. (AEC)

49 CFR 173.185 - Lithium cells and batteries.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 20 Wh for a lithium ion cell or 100 Wh for a lithium ion battery. After December 31, 2015, each lithium ion battery subject to this provision must be marked with the Watt-hour rating on the outside case... cell and 25 g for a lithium metal battery and 60 Wh for a lithium ion cell or 300 Wh for a lithium ion...

On the reasons for low sulphur utilization in the lithium-sulphur batteries

NASA Astrophysics Data System (ADS)

Kolosnitsyn, V. S.; Kuzmina, E. V.; Karaseva, E. V.

2015-01-01

This work is to study the reasons for the relatively low efficiency of sulphur reduction (about 75%) in lithium-sulphur batteries. The two main reasons for that are suggested to be: the relatively low electrochemical activity of low order lithium polysulphides and blocking of the carbon framework of the sulphur electrode by insoluble products of electrochemical reactions - sulphur and lithium sulphide. The electrochemical activity of lithium polysulphides with different composition (Li2Sn, n = 2-6) has been studied in 1 M solutions of CF3SO3Li in sulfolane. It is shown that lithium polysulphides including lithium disulphide are able to electrochemically reduce with efficiency close to 100%. The electrochemical activity of lithium polysulphides decreases with the order. The order of lithium polysulphides affects the value of voltage of discharge plateaus but not the efficiency of sulphur reducing in the lithium polysulphides species. The relatively low efficiency of sulphur reduction in the lithium-sulphur batteries is more likely caused by blocking of carbon particles in the sulphur electrode by insoluble products of electrochemical reactions (sulphur and lithium sulphide). This prevents the electrochemical reduction of low order lithium polysulphides and especially lithium disulphide.

A lithium–oxygen battery based on lithium superoxide

DOE PAGES

Lu, Jun; Jung Lee, Yun; Luo, Xiangyi; ...

2016-01-11

Batteries based on sodium superoxide and on potassium superoxide have recently been reported(1-3). But, there have been no reports of a battery based on lithium superoxide (LiO 2), despite much research(4-8) into the lithium-oxygen (Li-O 2) battery because of its potential high energy density. Several studies(9-16) of Li-O 2 batteries have found evidence of LiO 2 being formed as one component of the discharge product along with lithium peroxide (Li 2O 2). In addition, theoretical calculations have indicated that some forms of LiO 2 may have a long lifetime(17). Our studies also suggest that it might be possible to formmore » LiO 2 alone for use in a battery. However, solid LiO 2 has been difficult to synthesize in pure form(18) because it is thermodynamically unstable with respect to disproportionation, giving Li 2O 2 (refs 19, 20). We show that crystalline LiO 2 can be stabilized in a Li-O 2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li 2O 2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO 2. Our results demonstrate that the LiO 2 formed in the Li-O 2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We also anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO 2, which could open the way to high-energy-density batteries based on LiO 2 as well as to other possible uses of this compound, such as oxygen storage.« less

A lithium–oxygen battery based on lithium superoxide

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

Lu, Jun; Jung Lee, Yun; Luo, Xiangyi

Batteries based on sodium superoxide and on potassium superoxide have recently been reported(1-3). But, there have been no reports of a battery based on lithium superoxide (LiO 2), despite much research(4-8) into the lithium-oxygen (Li-O 2) battery because of its potential high energy density. Several studies(9-16) of Li-O 2 batteries have found evidence of LiO 2 being formed as one component of the discharge product along with lithium peroxide (Li 2O 2). In addition, theoretical calculations have indicated that some forms of LiO 2 may have a long lifetime(17). Our studies also suggest that it might be possible to formmore » LiO 2 alone for use in a battery. However, solid LiO 2 has been difficult to synthesize in pure form(18) because it is thermodynamically unstable with respect to disproportionation, giving Li 2O 2 (refs 19, 20). We show that crystalline LiO 2 can be stabilized in a Li-O 2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li 2O 2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO 2. Our results demonstrate that the LiO 2 formed in the Li-O 2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We also anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO 2, which could open the way to high-energy-density batteries based on LiO 2 as well as to other possible uses of this compound, such as oxygen storage.« less

Substitution of Li for Cu in Cu2ZnSnS4: Toward Wide Band Gap Absorbers with Low Cation Disorder for Thin Film Solar Cells.

PubMed

Lafond, A; Guillot-Deudon, C; Vidal, J; Paris, M; La, C; Jobic, S

2017-03-06

The substitution of lithium for copper in Cu 2 ZnSnS 4 (CZTS) has been experimentally and theoretically investigated. Formally, the (Cu 1-x Li x )ZnSnS 4 system exhibits two well-defined solid solutions. Indeed, single crystal structural analyses demonstrate that the low (x < 0.4) and high (x > 0.6) lithium-content compounds adopt the kesterite structure and the wurtz-kesterite structure, respectively. For x between 0.4 and 0.6, the two aforementioned structure types coexist. Moreover, 119 Sn NMR analyses carried out on a (Cu 0.7 Li 0.3 ) 2 ZnSnS 4 sample clearly indicate that lithium replaces copper preferentially on two of the three available 2-fold crystallographic sites commonly occupied by Cu and Zn in disordered kesterite. Furthermore, the observed individual lines in the NMR spectrum suggest that the propensity of Cu and Zn atoms to be randomly distributed over the 2c and 2d crystallographic sites is lowered when lithium is partially substituted for copper. Additionally, the first-principles calculations provide insights into the arrangement of Li atoms as a function of the Cu/Zn disorder and its effect on the structural (lattice parameters) and optical properties of CZTS (band gap evolution). Those calculations agree with the experimental observations and account for the evolutions of the unit cell parameters as well as for the increase of band gap when the Li-content increases. The calculation of the formation enthalpy of point defect unambiguously indicates that Li modifies the Cu/Zn disorder in a manner similar to the change of Cu/Zn disorder induced by Ag alloying. Overall, it was found that Li alloying is a versatile way of tuning the optoelectronic properties of CZTS making it a good candidate as wide band gap materials for the top cells of tandem solar cells.

High conducting oxide--sulfide composite lithium superionic conductor

DOEpatents

Liang, Chengdu; Rangasamy, Ezhiylmurugan; Dudney, Nancy J.; Keum, Jong Kahk; Rondinone, Adam Justin

2017-01-17

A solid electrolyte for a lithium-sulfur battery includes particles of a lithium ion conducting oxide composition embedded within a lithium ion conducting sulfide composition. The lithium ion conducting oxide composition can be Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO). The lithium ion conducting sulfide composition can be .beta.-Li.sub.3PS.sub.4 (LPS). A lithium ion battery and a method of making a solid electrolyte for a lithium ion battery are also disclosed.

Spreading of lithium on a stainless steel surface at room temperature

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

Skinner, C. H.; Capece, A. M.; Roszell, J. P.

Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. Here, the spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separatemore » experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (E des = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (E des = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium lithium bonding.« less

Spreading of lithium on a stainless steel surface at room temperature

DOE PAGES

Skinner, C. H.; Capece, A. M.; Roszell, J. P.; ...

2015-11-10

Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. Here, the spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separatemore » experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (E des = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (E des = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium lithium bonding.« less

Spreading of lithium on a stainless steel surface at room temperature

NASA Astrophysics Data System (ADS)

Skinner, C. H.; Capece, A. M.; Roszell, J. P.; Koel, B. E.

2016-01-01

Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. The spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separate experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (Edes = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (Edes = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium-lithium bonding.

Suppression of dendritic lithium growth in lithium metal-based batteries.

PubMed

Li, Linlin; Li, Siyuan; Lu, Yingying

2018-06-19

Lithium metal-based batteries offer promising prospects as alternatives to today's lithium-ion batteries, due to their ultra-high energy density. Unfortunately, the application of lithium metal is full of challenges and has puzzled researchers for more than 40 years. In this feature article, we describe the history of the development of lithium metal batteries and their existing key challenges, which include non-uniform electrodeposition, volume expansion, high reactivity of the lithium metal/unstable solid electrolyte interphase (SEI), and the shuttling of active cathode materials. Then, we focus on the growth mechanisms of uneven lithium electrodeposition and extend the discussion to the approaches to inhibit lithium dendrites. Finally, we discuss future directions that are expected to drive progress in the development of lithium metal batteries.

Toxicity, uptake, and mutagenicity of particulate and soluble nickel compounds.

PubMed Central

Fletcher, G G; Rossetto, F E; Turnbull, J D; Nieboer, E

1994-01-01

Toxicity testing in AS52 cells (24-hr exposures) gave LC50 values of 2 to 130 micrograms Ni/ml for particulate nickel compounds and 45 to 60 micrograms Ni/ml for water-soluble salts (NiCl2, NiSO4, Ni(CH3COO)2). The Ni(OH)2, NiCO3, and sulfides (Ni3S2, Ni7S6, "amorphous NiS") exhibited similar toxicities (LC50's of 2 to 8 micrograms Ni/ml), while three nickel oxides were more variable and less toxic (LC50's of 18 to 130 micrograms Ni/ml). Most compounds displayed nuclear to cytoplasmic nickel ratios of approximately 1:1.5 to 1:5 (except approximately 1:20 for nickel salts). At the LC50's, a 75-fold range in exposure levels occurred compared to a 10-fold range in cytoplasmic and nuclear nickel concentrations, [Ni]. Cellular nickel distribution indicated three groupings: inert compounds (green NiO, lithium nickel oxide, relatively low nuclear and cytosolic [Ni]); water-soluble salts (very low nuclear [Ni]; high cytosolic [Ni]), and slightly soluble compounds (relatively high cytosolic and nuclear [Ni]). Nickel compounds are considered to be only weak or equivocal mutagens. In this study, a low but significant increase in mutation rate at the gpt locus was shown. Although the results would not be sufficient to deem nickel compounds mutagenic by traditional criteria, characterization by PCR analysis indicated that the spontaneous and nickel-induced mutants exhibited different and compound-specific mutational spectra (thus confirming nickel compound involvement). The results reported illustrate some of the methodologic problems involved in testing "weak" mutagens and indicate that alternative approaches may be necessary in classifying the mutagenicity of nickel and other compounds. PMID:7843140

75 FR 9147 - Hazardous Materials: Transportation of Lithium Batteries

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-01

... for lithium metal batteries and lithium ion batteries were adopted into the UN Recommendations. The... regulations were revised to reflect this change. Adopt shipping descriptions for lithium ion batteries including lithium ion polymer batteries (UN3480), lithium ion batteries packed with equipment including...

77 FR 28259 - Mailings of Lithium Batteries

Federal Register 2010, 2011, 2012, 2013, 2014

2012-05-14

... containing lithium metal or lithium-ion cells or batteries and applies regardless of quantity, size, watt... ``lithium content'' for secondary lithium-ion batteries when describing maximum quantity limits. In addition...-ion (Rechargeable) Cells and Batteries [Revise 10.20.6 as follows:] Small consumer-type lithium-ion...

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

High performance discharges in the Lithium Tokamak eXperiment with liquid lithium walls

DOE PAGES

Schmitt, J. C.; Bell, R. E.; Boyle, D. P.; ...

2015-05-15

The first-ever successful operation of a tokamak with a large area (40% of the total plasma surface area) liquid lithium wall has been achieved in the Lithium Tokamak eXperiment (LTX). These results were obtained with a new, electron beam-based lithium evaporation system, which can deposit a lithium coating on the limiting wall of LTX in a five-minute period. Preliminary analyses of diamagnetic and other data for discharges operated with a liquid lithium wall indicate that confinement times increased by 10 x compared to discharges with helium-dispersed solid lithium coatings. Ohmic energy confinement times with fresh lithium walls, solid and liquid,more » exceed several relevant empirical scaling expressions. Spectroscopic analysis of the discharges indicates that oxygen levels in the discharges limited on liquid lithium walls were significantly reduced compared to discharges limited on solid lithium walls. Finally, Tokamak operations with a full liquid lithium wall (85% of the total plasma surface area) have recently started.« less

Grain Boundary Engineering of Lithium-Ion-Conducting Lithium Lanthanum Titanate for Lithium-Air Batteries

DTIC Science & Technology

2016-01-01

release; distribution is unlimited. 1 1. Introduction Lithium (Li)- ion batteries are currently one of the leading energy storage device technologies...ARL-TR-7584 ● JAN 2016 US Army Research Laboratory Grain Boundary Engineering of Lithium - Ion - Conducting Lithium Lanthanum...Titanate for Lithium -Air Batteries by Victoria L Blair, Claire V Weiss Brennan, and Joseph M Marsico Approved for public

Lithium use in batteries

USGS Publications Warehouse

Goonan, Thomas G.

2012-01-01

Lithium has a number of uses but one of the most valuable is as a component of high energy-density rechargeable lithium-ion batteries. Because of concerns over carbon dioxide footprint and increasing hydrocarbon fuel cost (reduced supply), lithium may become even more important in large batteries for powering all-electric and hybrid vehicles. It would take 1.4 to 3.0 kilograms of lithium equivalent (7.5 to 16.0 kilograms of lithium carbonate) to support a 40-mile trip in an electric vehicle before requiring recharge. This could create a large demand for lithium. Estimates of future lithium demand vary, based on numerous variables. Some of those variables include the potential for recycling, widespread public acceptance of electric vehicles, or the possibility of incentives for converting to lithium-ion-powered engines. Increased electric usage could cause electricity prices to increase. Because of reduced demand, hydrocarbon fuel prices would likely decrease, making hydrocarbon fuel more desirable. In 2009, 13 percent of worldwide lithium reserves, expressed in terms of contained lithium, were reported to be within hard rock mineral deposits, and 87 percent, within brine deposits. Most of the lithium recovered from brine came from Chile, with smaller amounts from China, Argentina, and the United States. Chile also has lithium mineral reserves, as does Australia. Another source of lithium is from recycled batteries. When lithium-ion batteries begin to power vehicles, it is expected that battery recycling rates will increase because vehicle battery recycling systems can be used to produce new lithium-ion batteries.

Carbon-Coated Na3.32 Fe2.34 (P2 O7 )2 Cathode Material for High-Rate and Long-Life Sodium-Ion Batteries.

PubMed

Chen, Mingzhe; Chen, Lingna; Hu, Zhe; Liu, Qiannan; Zhang, Binwei; Hu, Yuxiang; Gu, Qinfen; Wang, Jian-Li; Wang, Lian-Zhou; Guo, Xiaodong; Chou, Shu-Lei; Dou, Shi-Xue

2017-06-01

Rechargeable sodium-ion batteries are proposed as the most appropriate alternative to lithium batteries due to the fast consumption of the limited lithium resources. Due to their improved safety, polyanion framework compounds have recently gained attention as potential candidates. With the earth-abundant element Fe being the redox center, the uniform carbon-coated Na 3.32 Fe 2.34 (P 2 O 7 ) 2 /C composite represents a promising alternative for sodium-ion batteries. The electrochemical results show that the as-prepared Na 3.32 Fe 2.34 (P 2 O 7 ) 2 /C composite can deliver capacity of ≈100 mA h g -1 at 0.1 C (1 C = 120 mA g -1 ), with capacity retention of 92.3% at 0.5 C after 300 cycles. After adding fluoroethylene carbonate additive to the electrolyte, 89.6% of the initial capacity is maintained, even after 1100 cycles at 5 C. The electrochemical mechanism is systematically investigated via both in situ synchrotron X-ray diffraction and density functional theory calculations. The results show that the sodiation and desodiation are single-phase-transition processes with two 1D sodium paths, which facilitates fast ionic diffusion. A small volume change, nearly 100% first-cycle Coulombic efficiency, and a pseudocapacitance contribution are also demonstrated. This research indicates that this new compound could be a potential competitor for other iron-based cathode electrodes for application in large-scale Na rechargeable batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on Colloid Vibration Current in Aqueous Solution of Binary Surfactant Mixtures: Effects of Counterions and Hydrophobic Chains.

PubMed

Takata, Youichi; Hyono, Atsushi; Ohshima, Hiroyuki

2016-11-01

In order to elucidate an electroacoustic phenomenon of mixed micelles in an aqueous solution, we measured the colloid vibration current (CVI) in aqueous solutions of binary surfactant mixtures. Based on the thermodynamic treatment of critical micelle concentration (cmc) values determined by conductivity measurements, it was expected that dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium chloride (DTAC) molecules would mix ideally in the micelle. However, the micelle composition as evaluated from the CVI measurement, based on the linear dependence of the CVI value on the micelle composition, differed from the aforementioned ideality. Considering these observations, we concluded that the CVI measurement was more sensitive to the counterion distribution near the micelle surface, whereas the thermodynamically determined micelle composition included the counterions more loosely bound in the diffuse double layer due to the electroneutrality condition included in its assumption. On the other hand, the phase diagram illustrating micelle formation in the lithium dodecyl sulfate (LiDS) - lithium perfluorooctane sulfonate (LiFOS) mixture system showed a heteroazeotropic point arising from the stronger interactions between homologous surfactants than between heterologous ones. Although the concentration dependence of CVI values was expected to drastically change at a heteroazeotropic point due to the enormous variation in the density of the micelle core, the results showed a monotonous change, which suggests that the density of the micelle core varies continuously. By taking the partial molar volume of fluorocarbon compounds in the hydrocarbon compounds into account, the density of the micelle core was affected by the size of the micelle as well as its constituents.

Contrasting Effects of Lithium Chloride and CB1 Receptor Blockade on Enduring Changes in the Valuation of Reward.

PubMed

Hernandez, Giovanni; Bernstein, David; Schoenbaum, Geoffrey; Cheer, Joseph F

2011-01-01

When an organism responds for a reward, its learned behavior can be characterized as goal-directed or habitual based on whether or not it is susceptible to reward devaluation. Here, we evaluated whether instrumental responding for brain stimulation reward (BSR) can be devalued using a paradigm traditionally used for natural rewards. Rats were trained to lever press for BSR; afterward, BSR was paired with either lithium chloride (LiCl, 5 mg/kg, i.p.), a pro-emetic, or AM251, a CB1 receptor antagonist (3 mg/kg, i.p.) or the vehicle of these compounds. Pairings of BSR with these compounds and their vehicles were performed in a novel environment so that only unconditional effects of BSR would be affected by the pharmacological manipulations. Subsequently, in a probe test, all rats were returned in the drug-free state to the boxes where they had received training and instrumental responding was reassessed in the absence of BSR delivery. When compared to control, LiCl produced a significant decrease in the number of responses during the test session, whereas AM251 did not. These results show that instrumental responding for BSR is susceptible to devaluation, in accord with the proposal that this behavior is supported at least in part by associations between the response and the rewarding outcome. Further, they suggest that reward modulation observed in studies involving the use of CB1 receptor antagonists arises from changes in the organism's motivation rather than drug-induced changes in the intrinsic value of reward.

Characterization of pore and crystal structure of synthesized LiBOB with varying quality of raw materials as electrolyte for lithium-ion battery

NASA Astrophysics Data System (ADS)

Lestariningsih, Titik; Ratri, Christin Rina; Wigayati, Etty Marty; Sabrina, Qolby

2016-02-01

Characterization of pore structure and crystal structure of the LiB(C2O4)2H2O or LIBOB compound has been performed in this study. These recent years, research regarding LiBOB electrolyte salt have been performed using analytical-grade raw materials, therefore this research was aimed to synthesized LiBOB electrolyte salt using the cheaper and abundant technical-grade raw materials. Lithium hydroxide (LiOH), oxalic acid dihydrate (H2C2O4.2H2O), and boric acid (H3BO3) both in technical-grade and analytical-grade quality were used as raw materials for the synthesis of LiBOB. Crystal structure characterization results of synthesized LiBOB from both technical-grade and analytical-grade raw materials have shown the existence of LiBOB and LiBOB hydrate phase with orthorombic structure. These results were also confirmed by FT-IR analysis, which showed the functional groups of LiBOB compounds. SEM analysis results showed that synthesized LiBOB has spherical structure, while commercial LiBOB has cylindrical structure. Synthesized LiBOB has a similar pore size of commercial LiBOB, i.e. 19 nm (mesoporous material). Surface area of synthesized LiBOB from analytical-grade raw materials and technical-grade materials as well as commercial LIBOB were 88.556 m2/g, 41.524 m2/g, and 108.776 m2/g, respectively. EIS analysis results showed that synthesized LiBOB from technical-grade raw materials has lower conductivity than synthesized LiBOB from analytical-grade raw materials.

Sodium-ion batteries: present and future.

PubMed

Hwang, Jang-Yeon; Myung, Seung-Taek; Sun, Yang-Kook

2017-06-19

Energy production and storage technologies have attracted a great deal of attention for day-to-day applications. In recent decades, advances in lithium-ion battery (LIB) technology have improved living conditions around the globe. LIBs are used in most mobile electronic devices as well as in zero-emission electronic vehicles. However, there are increasing concerns regarding load leveling of renewable energy sources and the smart grid as well as the sustainability of lithium sources due to their limited availability and consequent expected price increase. Therefore, whether LIBs alone can satisfy the rising demand for small- and/or mid-to-large-format energy storage applications remains unclear. To mitigate these issues, recent research has focused on alternative energy storage systems. Sodium-ion batteries (SIBs) are considered as the best candidate power sources because sodium is widely available and exhibits similar chemistry to that of LIBs; therefore, SIBs are promising next-generation alternatives. Recently, sodiated layer transition metal oxides, phosphates and organic compounds have been introduced as cathode materials for SIBs. Simultaneously, recent developments have been facilitated by the use of select carbonaceous materials, transition metal oxides (or sulfides), and intermetallic and organic compounds as anodes for SIBs. Apart from electrode materials, suitable electrolytes, additives, and binders are equally important for the development of practical SIBs. Despite developments in electrode materials and other components, there remain several challenges, including cell design and electrode balancing, in the application of sodium ion cells. In this article, we summarize and discuss current research on materials and propose future directions for SIBs. This will provide important insights into scientific and practical issues in the development of SIBs.

Reversible Lithium Neurotoxicity: Review of the Literature

PubMed Central

Netto, Ivan

2012-01-01

Objective: Lithium neurotoxicity may be reversible or irreversible. Reversible lithium neurotoxicity has been defined as cases of lithium neurotoxicity in which patients recovered without any permanent neurologic sequelae, even after 2 months of an episode of lithium toxicity. Cases of reversible lithium neurotoxicity differ in clinical presentation from those of irreversible lithium neurotoxicity and have important implications in clinical practice. This review aims to study the clinical presentation of cases of reversible lithium neurotoxicity. Data Sources: A comprehensive electronic search was conducted in the following databases: MEDLINE (PubMed), 1950 to November 2010; PsycINFO, 1967 to November 2010; and SCOPUS (EMBASE), 1950 to November 2010. MEDLINE and PsycINFO were searched by using the OvidSP interface. Study Selection: A combination of the following search terms was used: lithium AND adverse effects AND central nervous system OR neurologic manifestation. Publications cited include articles concerned with reversible lithium neurotoxicity. Data Extraction: The age, sex, clinical features, diagnostic categories, lithium doses, serum lithium levels, precipitating factors, and preventive measures of 52 cases of reversible lithium neurotoxicity were extracted. Data Synthesis: Among the 52 cases of reversible lithium neurotoxicity, patients ranged in age from 10 to 80 years and a greater number were female (P = .008). Most patients had affective disorders, schizoaffective disorders, and/or depression (P < .001) and presented mainly with acute organic brain syndrome. In most cases, the therapeutic serum lithium levels were less than or equal to 1.5 mEq/L (P < .001), and dosage regimens were less than 2,000 mg/day. Specific drug combinations with lithium, underlying brain pathology, abnormal tissue levels, specific diagnostic categories, and elderly populations were some of the precipitating factors reported for reversible lithium neurotoxicity. The preventive measures were also described. Conclusions: Reversible lithium neurotoxicity presents with a certain clinical profile and precipitating factors for which there are appropriate preventive measures. This recognition will help in early diagnosis and prompt treatment of lithium neurotoxicity. PMID:22690368

Towards a Unified Understanding of Lithium Action in Basic Biology and its Significance for Applied Biology.

PubMed

Jakobsson, Eric; Argüello-Miranda, Orlando; Chiu, See-Wing; Fazal, Zeeshan; Kruczek, James; Nunez-Corrales, Santiago; Pandit, Sagar; Pritchet, Laura

2017-12-01

Lithium has literally been everywhere forever, since it is one of the three elements created in the Big Bang. Lithium concentration in rocks, soil, and fresh water is highly variable from place to place, and has varied widely in specific regions over evolutionary and geologic time. The biological effects of lithium are many and varied. Based on experiments in which animals are deprived of lithium, lithium is an essential nutrient. At the other extreme, at lithium ingestion sufficient to raise blood concentration significantly over 1 mM/, lithium is acutely toxic. There is no consensus regarding optimum levels of lithium intake for populations or individuals-with the single exception that lithium is a generally accepted first-line therapy for bipolar disorder, and specific dosage guidelines for sufferers of that condition are generally agreed on. Epidemiological evidence correlating various markers of social dysfunction and disease vs. lithium level in drinking water suggest benefits of moderately elevated lithium compared to average levels of lithium intake. In contrast to other biologically significant ions, lithium is unusual in not having its concentration in fluids of multicellular animals closely regulated. For hydrogen ions, sodium ions, potassium ions, calcium ions, chloride ions, and magnesium ions, blood and extracellular fluid concentrations are closely and necessarily regulated by systems of highly selective channels, and primary and secondary active transporters. Lithium, while having strong biological activity, is tolerated over body fluid concentrations ranging over many orders of magnitude. The lack of biological regulation of lithium appears due to lack of lithium-specific binding sites and selectivity filters. Rather lithium exerts its myriad physiological and biochemical effects by competing for macromolecular sites that are relatively specific for other cations, most especially for sodium and magnesium. This review will consider what is known about the nature of this competition and suggest using and extending this knowledge towards the goal of a unified understanding of lithium in biology and the application of that understanding in medicine and nutrition.

ASSESSMENT OF LITHIUM USING THE IEHR EVALUATIVE PROCESS FOR ASSESSING HUMAN DEVELOPMENTAL AND REPRODUCTIVE TOXICITY OF AGENTS

EPA Science Inventory

This document presents an evaluation of the reproductive and developmental effects of lithium and reviews toxicologic information on several specific lithium salts: ithium carbonate, lithium chloride, lithium citrate, and lithium hypochlorite. ithium (Li), an alkali metal, is a n...

77 FR 68069 - Outbound International Mailings of Lithium Batteries

Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-15

... (Rechargeable) Cells and Batteries Small consumer-type lithium-ion cells and batteries like those used to power... of only four lithium-ion cells or two lithium-ion batteries. c. The lithium content must not exceed... POSTAL SERVICE 39 CFR Part 20 Outbound International Mailings of Lithium Batteries AGENCY: Postal...

77 FR 28488 - Outbound International Mailings of Lithium Batteries and Other Dangerous Goods

Federal Register 2010, 2011, 2012, 2013, 2014

2012-05-15

... Instructions. Lithium-ion cells and lithium metal batteries are listed in the Technical Instructions as Class 9... metal or lithium alloy (non-rechargeable) cells and batteries, or secondary lithium-ion cells and... POSTAL SERVICE 39 CFR Part 20 Outbound International Mailings of Lithium Batteries and Other...

Lithium Down-regulates Histone Deacetylase 1 (HDAC1) and Induces Degradation of Mutant Huntingtin*

PubMed Central

Wu, Shuai; Zheng, Shui-Di; Huang, Hong-Ling; Yan, Li-Chong; Yin, Xiao-Fei; Xu, Hai-Neng; Zhang, Kang-Jian; Gui, Jing-Hua; Chu, Liang; Liu, Xin-Yuan

2013-01-01

Lithium is an effective mood stabilizer that has been clinically used to treat bipolar disorder for several decades. Recent studies have suggested that lithium possesses robust neuroprotective and anti-tumor properties. Thus far, a large number of lithium targets have been discovered. Here, we report for the first time that HDAC1 is a target of lithium. Lithium significantly down-regulated HDAC1 at the translational level by targeting HDAC1 mRNA. We also showed that depletion of HDAC1 is essential for the neuroprotective effects of lithium and for the lithium-mediated degradation of mutant huntingtin through the autophagic pathway. Our studies explain the multiple functions of lithium and reveal a novel mechanism for the function of lithium in neurodegeneration. PMID:24165128

Where is the lithium? Quantitative determination of the lithium distribution in lithium ion battery cells: Investigations on the influence of the temperature, the C-rate and the cell type

NASA Astrophysics Data System (ADS)

Vortmann-Westhoven, Britta; Winter, Martin; Nowak, Sascha

2017-04-01

With lithium being the capacity determining species in lithium-ion battery (LIB) cells, the local quantification is of enormous importance for understanding of the cell performance. The investigation of the lithium distribution in LIB full cells is performed with two different cell types, T-cells of the Swagelok® type and pouch bag cells with lithium nickel cobalt manganese oxide and mesocarbon microbead graphite as the active materials as well as a lithium hexafluorophosphate based organic carbonate solvent electrolyte. The lithium content of/at the individual components of the cells is analyzed for different states of charge (SOCs) by inductively coupled plasma-optical emission spectrometry (ICP-OES) and the lithium distribution as well as the loss of active lithium within the cells is calculated after cycling. With increasing the SOC, the lithium contents decrease in the cathodes and simultaneously increase in the anodes. The temperature increase shows a clear shift of the lithium content in the direction of the anode for the T-cells. The comparison of the C-rate influence shows that the lower the C-rate, the more the lithium content on the electrodes is shifted into the direction of the anode.

Antidepressant-like Responses to Lithium in Genetically Diverse Mouse Strains

PubMed Central

Can, Adem; Blackwell, Robert A.; Piantadosi, Sean C.; Dao, David T.; O’Donnell, Kelley C.; Gould, Todd D.

2011-01-01

A mood stabilizing and antidepressant response to lithium is only found in a subgroup of bipolar disorder and depression patients. Identifying strains of mice that are responsive and non-responsive to lithium may elucidate genomic and other biological factors that play a role in lithium responsiveness. Mouse strains were tested in the forced swim, tail suspension, and open field tests after acute and chronic systemic, and intracerebroventricular and chronic lithium treatments. Serum and brain lithium levels were measured. Three (129S6/SvEvTac, C3H/HeNHsd, C57BL/6J) of the eight inbred strains tested, and one (CD-1) of the three outbred strains, showed an antidepressant-like response in the forced swim test following acute systemic administration of lithium. The three responsive inbred strains, as well as the DBA/2J strain, were also responsive in the forced swim test after chronic administration of lithium. However, in the tail suspension test, acute lithium resulted in an antidepressant-like effect only in C3H/HeNHsd mice. Only C57BL/6J and DBA/2J were responsive in the tail suspension test after chronic administration of lithium. Intracerebroventricular lithium administration resulted in a similar response profile in BALB/cJ (non-responsive) and C57BL/6J (responsive) strains. Serum and brain lithium concentrations demonstrated that behavioral results were not due to differential pharmacokinetics of lithium in individual strains, suggesting that genetic factors likely regulate responsiveness to lithium. Our results indicate that responsiveness to lithium in tests of antidepressant efficacy varies among genetically diverse mouse strains. These results will assist in identifying genomic factors associated with lithium responsiveness and the mechanisms of lithium action. PMID:21306560

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

PubMed

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

2017-08-16

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

Reasons for lithium discontinuation in men and women with bipolar disorder: a retrospective cohort study.

PubMed

Öhlund, Louise; Ott, Michael; Oja, Sofia; Bergqvist, Malin; Lundqvist, Robert; Sandlund, Mikael; Salander Renberg, Ellinor; Werneke, Ursula

2018-02-07

Lithium remains first choice as maintenance treatment for bipolar affective disorder. Yet, about half of all individuals may stop their treatment at some point, despite lithium's proven benefits concerning the prevention of severe affective episodes and suicide. Retrospective cohort study in the Swedish region of Norrbotten into the causes of lithium discontinuation. The study was set up to (1) test whether patients with bipolar affective disorder or schizoaffective disorder, treated with lithium maintenance therapy, were more likely to discontinue lithium because of adverse effects than lack of therapeutic effectiveness, (2) explore gender differences, (3) understand the role of diagnosis and (4) identify who, patient or doctor, took the initiative to stop lithium. Review of medical records for all episodes of lithium discontinuation that had occurred between 1997 and 2013 with the intent to stop lithium for good. Of 873 patients treated with lithium, 54% discontinued lithium, corresponding to 561 episodes of lithium discontinuation. In 62% of episodes, lithium was discontinued due to adverse effects, in 44% due to psychiatric reasons, and in 12% due to physical reasons interfering with lithium treatment. The five single most common adverse effects leading to lithium discontinuation were diarrhoea (13%), tremor (11%), polyuria/polydipsia/diabetes insipidus (9%), creatinine increase (9%) and weight gain (7%). Women were as likely as men to take the initiative to stop lithium, but twice as likely to consult a doctor before taking action (p < 0.01). Patients with type 1 BPAD or SZD were more likely to discontinue lithium than patients with type 2 or unspecified BPAD (p < 0.01). Patients with type 1 BPAD or SZD were more likely to refuse medication (p < 0.01). Conversely, patients with type 2 or unspecified BPAD were three times as likely to discontinue lithium for lack or perceived lack of effectiveness (p < 0.001). Stopping lithium treatment is common and occurs mostly due to adverse effects. It is important to discuss potential adverse effects with patients before initiation and continuously during lithium treatment, to reduce the frequency of potentially unnecessary discontinuations.

Multi-layered, chemically bonded lithium-ion and lithium/air batteries

DOEpatents

Narula, Chaitanya Kumar; Nanda, Jagjit; Bischoff, Brian L; Bhave, Ramesh R

2014-05-13

Disclosed are multilayer, porous, thin-layered lithium-ion batteries that include an inorganic separator as a thin layer that is chemically bonded to surfaces of positive and negative electrode layers. Thus, in such disclosed lithium-ion batteries, the electrodes and separator are made to form non-discrete (i.e., integral) thin layers. Also disclosed are methods of fabricating integrally connected, thin, multilayer lithium batteries including lithium-ion and lithium/air batteries.

A prospective comparative study of interaction between lithium and modified electroconvulsive therapy.

PubMed

Thirthalli, Jagadisha; Harish, Thippeswamy; Gangadhar, Bangalore N

2011-03-01

To compare patients on lithium and those not on lithium with regard to adverse effects while receiving ECT. Inpatients with schizophrenia, non-organic psychosis, mania and depression, who were prescribed ECTs either on (n=27) or not (n=28) on lithium were studied. Clinicians blind to lithium-status recorded seizure parameters, interaction with succinyl choline, cardiovascular response, recovery from ECT and immediate post-ECT complications. The lithium group showed no significant difference in terms of seizure variables, apnea time, and recovery from anaesthesia when compared to the non-lithium group. Average maximum heart rate, average maximum systolic blood pressure and average maximum rate pressure product were significantly lower in patients who had combined lithium and ECT. In lithium patients the average time to post-ECT recovery was directly correlated with serum lithium level. Though concurrent lithium is by and large safe during ECT, it benefits to maintain serum lithium level at lower end of therapeutic range. However, the findings can be applied to relatively young patients with no risk factors for ECT-complications.

Population Pharmacokinetic Analyses of Lithium: A Systematic Review.

PubMed

Methaneethorn, Janthima

2018-02-01

Even though lithium has been used for the treatment of bipolar disorder for several decades, its toxicities are still being reported. The major limitation in the use of lithium is its narrow therapeutic window. Several methods have been proposed to predict lithium doses essential to attain therapeutic levels. One of the methods used to guide lithium therapy is population pharmacokinetic approach which accounts for inter- and intra-individual variability in predicting lithium doses. Several population pharmacokinetic studies of lithium have been conducted. The objective of this review is to provide information on population pharmacokinetics of lithium focusing on nonlinear mixed effect modeling approach and to summarize significant factors affecting lithium pharmacokinetics. A literature search was conducted from PubMed database from inception to December, 2016. Studies conducted in humans, using lithium as a study drug, providing population pharmacokinetic analyses of lithium by means of nonlinear mixed effect modeling, were included in this review. Twenty-four articles were identified from the database. Seventeen articles were excluded based on the inclusion and exclusion criteria. A total of seven articles were included in this review. Of these, only one study reported a combined population pharmacokinetic-pharmacodynamic model of lithium. Lithium pharmacokinetics were explained using both one- and two-compartment models. The significant predictors of lithium clearance identified in most studies were renal function and body size. One study reported a significant effect of age on lithium clearance. The typical values of lithium clearance ranged from 0.41 to 9.39 L/h. The magnitude of inter-individual variability on lithium clearance ranged from 12.7 to 25.1%. Only two studies evaluated the models using external data sets. Model methodologies in each study are summarized and discussed in this review. For future perspective, a population pharmacokinetic-pharmacodynamic study of lithium is recommended. Moreover, external validation of previously published models should be performed.

A low-temperature electrolyte for lithium and lithium-ion batteries

NASA Astrophysics Data System (ADS)

Plichta, E. J.; Behl, W. K.

An electrolyte consisting of 1 M solution of lithium hexafluorophosphate in 1:1:1 ethylene carbonate(EC)-dimethyl carbonate(DMC)-ethyl methyl carbonate(EMC) is proposed for low temperature applications of lithium and lithium-ion cells. The new electrolyte has good conductivity and electrochemical stability. Lithium and lithium-ion cells using the new electrolyte were found to be operable at temperatures down to -40°C. The paper also reports on the electrochemical stability of aluminum metal, which is used as a substrate for the positive electrodes in lithium-ion cells, in the new electrolyte.

Lithium-associated hyperthyroidism.

PubMed

Siyam, Fadi F; Deshmukh, Sanaa; Garcia-Touza, Mariana

2013-08-01

Goiters and hypothyroidism are well-known patient complications of the use of lithium for treatment of bipolar disease. However, the occurrence of lithium-induced hyperthyroidism is a more rare event. Many times, the condition can be confused with a flare of mania. Monitoring through serial biochemical measurement of thyroid function is critical in patients taking lithium. Hyperthyroidism induced by lithium is a condition that generally can be controlled medically without the patient having to discontinue lithium therapy, although in some circumstances, discontinuation of lithium therapy may be indicated. We report on a patient case of lithium-associated hyperthyroidism that resolved after discontinuation of the medication.

Tracking Lithium Ions via Widefield Fluorescence Microscopy for Battery Diagnostics.

PubMed

Padilla, Nicolas A; Rea, Morgan T; Foy, Michael; Upadhyay, Sunil P; Desrochers, Kyle A; Derus, Tyler; Knapper, Kassandra A; Hunter, Nathanael H; Wood, Sharla; Hinton, Daniel A; Cavell, Andrew C; Masias, Alvaro G; Goldsmith, Randall H

2017-07-28

Direct tracking of lithium ions with time and spatial resolution can provide an important diagnostic tool for understanding mechanisms in lithium ion batteries. A fluorescent indicator of lithium ions, 2-(2-hydroxyphenyl)naphthoxazole, was synthesized and used for real-time tracking of lithium ions via widefield fluorescence microscopy. The fluorophore can be excited with visible light and was shown to enable quantitative determination of the lithium ion diffusion constant in a microfluidic model system for a plasticized polymer electrolyte lithium battery. The use of widefield fluorescence microscopy for in situ tracking of lithium ions in batteries is discussed.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

PubMed Central

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-01-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level. PMID:28272396

Oriented TiO2 nanotubes as a lithium metal storage medium

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

Kim, Jae-Hun; Kang, Hee-Kook; Woo, Sang-Gil

2014-07-01

A new strategy for suppressing dendritic lithium growth in rechargeable lithium metal batteries is introduced, in which TiO2 nanotube (NT) array electrodes prepared by anodization are used as a metallic lithium storage medium. During the first charge process, lithium ions are inserted into the crystal structure of the TiO2 NT arrays, and then, lithium metal is deposited on the surfaces of the NT arrays, i.e., in the NT pores and between NT walls. From the second cycle onward, the TiO2 material is used as lithium ion pathways, which results in the effective current distribution for lithium deposition and prevents disintegrationmore » of the deposited metallic lithium. Compared to a Li(Cu foil)-LiCoO2 cell, the Li(TiO2 NT)-LiCoO2 cell exhibits enhanced cycling efficiency. This new concept will enable other 3D structured negative active materials to be used as lithium metal storage media for lithium metal batteries.« less

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

NASA Astrophysics Data System (ADS)

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion...carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery.

PubMed

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-08

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Solid-state lithium battery

DOEpatents

Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross

2014-11-04

The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

Lithium vanadium oxides (Li1+xV3O8) as cathode materials in lithium-ion batteries for soldier portable power systems

NASA Astrophysics Data System (ADS)

Wang, Gaojun; Chen, Linfeng; Mathur, Gyanesh N.; Varadan, Vijay K.

2011-04-01

Improving soldier portable power systems is very important for saving soldiers' lives and having a strategic advantage in a war. This paper reports our work on synthesizing lithium vanadium oxides (Li1+xV3O8) and developing their applications as the cathode (positive) materials in lithium-ion batteries for soldier portable power systems. Two synthesizing methods, solid-state reaction method and sol-gel method, are used in synthesizing lithium vanadium oxides, and the chemical reaction conditions are determined mainly based on thermogravimetric and differential thermogravimetric (TG-DTG) analysis. The synthesized lithium vanadium oxides are used as the active positive materials in the cathodes of prototype lithium-ion batteries. By using the new solid-state reaction technique proposed in this paper, lithium vanadium oxides can be synthesized at a lower temperature and in a shorter time, and the synthesized lithium vanadium oxide powders exhibit good crystal structures and good electrochemical properties. In the sol-gel method, different lithium source materials are used, and it is found that lithium nitrate (LiNO3) is better than lithium carbonate (Li2CO3) and lithium hydroxide (LiOH). The lithium vanadium oxides synthesized in this work have high specific charge and discharge capacities, which are helpful for reducing the sizes and weights, or increasing the power capacities, of soldier portable power systems.

What we need to know about the effect of lithium on the kidney.

PubMed

Gong, Rujun; Wang, Pei; Dworkin, Lance

2016-12-01

Lithium has been a valuable treatment for bipolar affective disorders for decades. Clinical use of lithium, however, has been problematic due to its narrow therapeutic index and concerns for its toxicity in various organ systems. Renal side effects associated with lithium include polyuria, nephrogenic diabetes insipidus, proteinuria, distal renal tubular acidosis, and reduction in glomerular filtration rate. Histologically, chronic lithium nephrotoxicity is characterized by interstitial nephritis with microcyst formation and occasional focal segmental glomerulosclerosis. Nevertheless, this type of toxicity is uncommon, with the strongest risk factors being high serum levels of lithium and longer time on lithium therapy. In contrast, in experimental models of acute kidney injury and glomerular disease, lithium has antiproteinuric, kidney protective, and reparative effects. This paradox may be partially explained by lower lithium doses and short duration of therapy. While long-term exposure to higher psychiatric doses of lithium may be nephrotoxic, short-term low dose of lithium may be beneficial and ameliorate kidney and podocyte injury. Mechanistically, lithium targets glycogen synthase kinase-3β, a ubiquitously expressed serine/threonine protein kinase implicated in the processes of tissue injury, repair, and regeneration in multiple organ systems, including the kidney. Future studies are warranted to discover the exact "kidney-protective dose" of lithium and test the effects of low-dose lithium on acute and chronic kidney disease in humans. Copyright © 2016 the American Physiological Society.

What we need to know about the effect of lithium on the kidney

PubMed Central

Gong, Rujun; Wang, Pei

2016-01-01

Lithium has been a valuable treatment for bipolar affective disorders for decades. Clinical use of lithium, however, has been problematic due to its narrow therapeutic index and concerns for its toxicity in various organ systems. Renal side effects associated with lithium include polyuria, nephrogenic diabetes insipidus, proteinuria, distal renal tubular acidosis, and reduction in glomerular filtration rate. Histologically, chronic lithium nephrotoxicity is characterized by interstitial nephritis with microcyst formation and occasional focal segmental glomerulosclerosis. Nevertheless, this type of toxicity is uncommon, with the strongest risk factors being high serum levels of lithium and longer time on lithium therapy. In contrast, in experimental models of acute kidney injury and glomerular disease, lithium has antiproteinuric, kidney protective, and reparative effects. This paradox may be partially explained by lower lithium doses and short duration of therapy. While long-term exposure to higher psychiatric doses of lithium may be nephrotoxic, short-term low dose of lithium may be beneficial and ameliorate kidney and podocyte injury. Mechanistically, lithium targets glycogen synthase kinase-3β, a ubiquitously expressed serine/threonine protein kinase implicated in the processes of tissue injury, repair, and regeneration in multiple organ systems, including the kidney. Future studies are warranted to discover the exact “kidney-protective dose” of lithium and test the effects of low-dose lithium on acute and chronic kidney disease in humans. PMID:27122541

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries.

PubMed

Luo, Chao; Xu, Gui-Liang; Ji, Xiao; Hou, Singyuk; Chen, Long; Wang, Fei; Jiang, Jianjun; Chen, Zonghai; Ren, Yang; Amine, Khalil; Wang, Chunsheng

2018-03-05

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAh g -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAh g -1 can be retained for 2000 cycles, demonstrating excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na + . The reversible redox chemistry between azo compound and Na ions offer opportunities for developing long-cycle-life and high-rate SSIBs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

49 CFR 173.185 - Lithium cells and batteries.

Code of Federal Regulations, 2012 CFR

2012-10-01

... Class 7 § 173.185 Lithium cells and batteries. (a) Cells and batteries. A lithium cell or battery, including a lithium polymer cell or battery and a lithium-ion cell or battery, must conform to all of the... 49 Transportation 2 2012-10-01 2012-10-01 false Lithium cells and batteries. 173.185 Section 173...

49 CFR 173.185 - Lithium cells and batteries.

Code of Federal Regulations, 2013 CFR

2013-10-01

... Class 7 § 173.185 Lithium cells and batteries. (a) Cells and batteries. A lithium cell or battery, including a lithium polymer cell or battery and a lithium-ion cell or battery, must conform to all of the... 49 Transportation 2 2013-10-01 2013-10-01 false Lithium cells and batteries. 173.185 Section 173...

49 CFR 173.185 - Lithium cells and batteries.

Code of Federal Regulations, 2011 CFR

2011-10-01

... Class 7 § 173.185 Lithium cells and batteries. (a) Cells and batteries. A lithium cell or battery, including a lithium polymer cell or battery and a lithium-ion cell or battery, must conform to all of the... 49 Transportation 2 2011-10-01 2011-10-01 false Lithium cells and batteries. 173.185 Section 173...

49 CFR 173.185 - Lithium cells and batteries.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Class 7 § 173.185 Lithium cells and batteries. (a) Cells and batteries. A lithium cell or battery, including a lithium polymer cell or battery and a lithium-ion cell or battery, must conform to all of the... 49 Transportation 2 2010-10-01 2010-10-01 false Lithium cells and batteries. 173.185 Section 173...

Determination of theoretical capacity of metal ion-doped LiMn 2O 4 as the positive electrode in Li-ion batteries

NASA Astrophysics Data System (ADS)

Todorov, Yanko M.; Hideshima, Yasufumi; Noguchi, Hideyuki; Yoshio, Masaki

The theoretical capacity and cation vacancy of metal ion (M)-doped LiMn 2- xM xO 4 spinel compounds serving as positive electrodes in a 4-V lithium ion batteries are calculated. The capacity depends strongly on the mole fraction of doped metal ion and vacancies. The theoretical capacity increases with increasing oxidation number of the doped metal ion in the 16d site of LiMn 2O 4 at the same doping fraction. The validity of the proposed equation for calculation of the capacity has been initially confirmed using a metal ion with well-known valence, such as the Al ion. The oxidation state of Co, Ni and Cr ions in the spinel structure is found to be trivalent, divalent and trivalent, respectively. Analysis shows that metal ion-doped spinel compounds with low vacancy content promote high capacity.

Neutral six-coordinate bis(dithiocarbamato)silicon(iv) complexes with an SiCl2S4 skeleton.

PubMed

Baus, Johannes A; Tacke, Reinhold

2017-07-11

Treatment of SiCl 4 with lithium dithiocarbamates of the formula type Li[R 2 NCS 2 ] (R = Ph, iPr) in a molar ratio of 1 : 2 afforded the respective six-coordinate silicon(iv) complexes [Ph 2 NCS 2 ] 2 SiCl 2 (3) and [iPr 2 NCS 2 ] 2 SiCl 2 (4), which were isolated as the solvates 3·MeCN and 4·MeCN. Compounds 3·MeCN and 4·MeCN were structurally characterised by single-crystal X-ray diffraction and multinuclear NMR spectroscopic studies in the solid state and in solution. In this study, dithiocarbamato ligands were implemented in silicon coordination chemistry for the first time. Compounds 3 and 4 represent the first six-coordinate silicon(iv) complexes with an SiCl 2 S 4 skeleton.

Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Shrestha, Yesha

2016-01-01

There are 63 chemical elements that have two or more isotopes that are used to determine their standard atomic weights. The isotopic abundances and atomic weights of these elements can vary in normal materials due to physical and chemical fractionation processes (not due to radioactive decay). These variations are well known for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium), and the standard atomic weight of each of these elements is given by IUPAC as an interval with lower and upper bounds. Graphical plots of selected materials and compounds of each of these elements have been published previously. Herein and at the URL http://dx.doi.org/10.5066/F7GF0RN2, we provide isotopic abundances, isotope-delta values, and atomic weights for each of the upper and lower bounds of these materials and compounds.

Lithium toxicity in a neonate owing to false elevation of blood lithium levels caused by contamination in a lithium heparin container: case report and review of the literature.

PubMed

Arslan, Zainab; Athiraman, Naveen K; Clark, Simon J

2016-08-01

Lithium toxicity in a neonate can occur owing to antenatal exposure as a result of maternal treatment for psychiatric illnesses. False elevation of lithium levels has been reported in the paediatric population when the sample was mistakenly collected in a lithium heparin container. A term, male infant was born to a mother who was on lithium treatment for a psychiatric illness. On day 1, the infant was jittery, had a poor suck with difficulties in establishing feeds. Blood taken from the infant approximately 8 hours after birth demonstrated a lithium level of 4.9 mmol/L (adult toxic level w1.5 mmol/L). However, the sample for lithium levels was sent in a lithium heparin container and the probability of false elevation was considered. He was closely monitored in the neonatal intensive care unit and his hydration was optimised with intravenous fluids. Clinically, he remained well and commenced feeding, and his jitteriness had decreased the following day. A repeat blood lithium level, collected in a gel container, was only 0.4 mmol/L. The initially raised lithium level was owing to contamination from the lithium heparin container.

Neuroprotective Effects of Psychotropic Drugs in Huntington’s Disease

PubMed Central

Lauterbach, Edward C.

2013-01-01

Psychotropics (antipsychotics, mood stabilizers, antidepressants, anxiolytics, etc.) are commonly prescribed to treat Huntington’s disease (HD). In HD preclinical models, while no psychotropic has convincingly affected huntingtin gene, HD modifying gene, or huntingtin protein expression, psychotropic neuroprotective effects include upregulated huntingtin autophagy (lithium), histone acetylation (lithium, valproate, lamotrigine), miR-222 (lithium-plus-valproate), mitochondrial protection (haloperidol, trifluoperazine, imipramine, desipramine, nortriptyline, maprotiline, trazodone, sertraline, venlafaxine, melatonin), neurogenesis (lithium, valproate, fluoxetine, sertraline), and BDNF (lithium, valproate, sertraline) and downregulated AP-1 DNA binding (lithium), p53 (lithium), huntingtin aggregation (antipsychotics, lithium), and apoptosis (trifluoperazine, loxapine, lithium, desipramine, nortriptyline, maprotiline, cyproheptadine, melatonin). In HD live mouse models, delayed disease onset (nortriptyline, melatonin), striatal preservation (haloperidol, tetrabenazine, lithium, sertraline), memory preservation (imipramine, trazodone, fluoxetine, sertraline, venlafaxine), motor improvement (tetrabenazine, lithium, valproate, imipramine, nortriptyline, trazodone, sertraline, venlafaxine), and extended survival (lithium, valproate, sertraline, melatonin) have been documented. Upregulated CREB binding protein (CBP; valproate, dextromethorphan) and downregulated histone deacetylase (HDAC; valproate) await demonstration in HD models. Most preclinical findings await replication and their limitations are reviewed. The most promising findings involve replicated striatal neuroprotection and phenotypic disease modification in transgenic mice for tetrabenazine and for sertraline. Clinical data consist of an uncontrolled lithium case series (n = 3) suggesting non-progression and a primarily negative double-blind, placebo-controlled clinical trial of lamotrigine. PMID:24248060

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.

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

PubMed Central

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

PubMed

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

2017-04-10

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

Lithium-Based High Energy Density Flow Batteries

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

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.

Dendrite preventing separator for secondary lithium batteries

NASA Technical Reports Server (NTRS)

Shen, David H. (Inventor); Surampudi, Subbarao (Inventor); Huang, Chen-Kuo (Inventor); Halpert, Gerald (Inventor)

1993-01-01

Dendrites are prevented from shorting a secondary lithium battery by use of a first porous separator, such as porous polypropylene, adjacent to the lithium anode that is unreactive with lithium and a second porous fluoropolymer separator between the cathode and the first separator, such as polytetrafluoroethylene, that is reactive with lithium. As the tip of a lithium dendrite contacts the second separator, an exothermic reaction occurs locally between the lithium dendrite and the fluoropolymer separator. This results in the prevention of the dendrite propagation to the cathode.

Dendrite preventing separator for secondary lithium batteries

NASA Technical Reports Server (NTRS)

Shen, David H. (Inventor); Surampudi, Subbarao (Inventor); Huang, Chen-Kuo (Inventor); Halpert, Gerald (Inventor)

1995-01-01

Dendrites are prevented from shorting a secondary lithium battery by use of a first porous separator such as porous polypropylene adjacent the lithium anode that is unreactive with lithium and a second porous fluoropolymer separator between the cathode and the first separator such as polytetrafluoroethylene that is reactive with lithium. As the tip of a lithium dendrite contacts the second separator, an exothermic reaction occurs locally between the lithium dendrite and the fluoropolymer separator. This results in the prevention of the dendrite propagation to the cathode.

A Survey of Low-Temperature Operational Boundaries of Navy and Marine Corps Lithium and Lithium-Ion Batteries

DTIC Science & Technology

2016-09-29

Lithium and Lithium - Ion Batteries September 29, 2016 Approved for public release; distribution is unlimited. Joseph F. parker JeFFrey W. Long Surface...Boundaries of Navy and Marine Corps Lithium and Lithium - Ion Batteries Joseph F. Parker, Jeffrey W. Long, Olga A. Baturina, and Corey T. Love Naval...U.S. Marine Corps have identified a strategic interest to operate lithium - ion batteries in cold climate regions as well as undersea and in high

Lithium compensation for full cell operation

DOEpatents

Xiao, Jie; Zheng, Jianming; Chen, Xilin; Lu, Dongping; Liu, Jun; Jiguang, Jiguang

2016-05-17

Disclosed herein are embodiments of a lithium-ion battery system comprising an anode, an anode current collector, and a layer of lithium metal in contact with the current collector, but not in contact with the anode. The lithium compensation layer dissolves into the electrolyte to compensate for the loss of lithium ions during usage of the full cell. The specific placement of the lithium compensation layer, such that there is no direct physical contact between the lithium compensation layer and the anode, provides certain advantages.

Solid state neutron detector and method for use

DOEpatents

Doty, F. Patrick; Zwieback, Ilya; Ruderman, Warren

2002-01-01

Crystals of lithium tetraborate or alpha-barium borate had been found to be neutron detecting materials. The crystals are prepared using known crystal growing techniques, wherein the process does not include the common practice of using a fluxing agent, such as sodium oxide or sodium fluoride, to reduce the melting temperature of the crystalline compound. Crystals prepared by this method can be sliced into thin single or polycrystalline wafers, or ground to a powder and prepared as a sintered compact or a print paste, and then configured with appropriate electronic hardware, in order to function as neutron detectors.

Soluble, Highly Conjugated Derivatives of Polyacetylene from the Ring-Opening Metathesis Polymerization of Monosubstituted Cyclooctatetraenes: Synthesis and the Relationship Between Polymer Structure and Physical Properties

DTIC Science & Technology

1993-01-15

through a pad of Celite into a flask equipped with a sidearm stopcock and the volume of the solution was not adjusted. Neopentyl lithium was...The resonance at 2.5 ppm (A) was irradiated and both this resonance and the resonance at 2.8 ppm (B) were integrated. An ethylene glycol temperature...angles for different side groups in model compound S (MM2 results, C3 = cyclopropyl, Np = neopentyl ). Figure 14. Values of torsion angle el at 10 fs

Test of level density models from reactions of Li6 on Fe58 and Li7 on Fe57

NASA Astrophysics Data System (ADS)

Oginni, B. M.; Grimes, S. M.; Voinov, A. V.; Adekola, A. S.; Brune, C. R.; Carter, D. E.; Heinen, Z.; Jacobs, D.; Massey, T. N.; O'Donnell, J. E.; Schiller, A.

2009-09-01

The reactions of Li6 on Fe58 and Li7 on Fe57 have been studied at 15 MeV beam energy. These two reactions produce the same compound nucleus, Cu64. The charged particle spectra were measured at backward angles. The data obtained have been compared with Hauser-Feshbach model calculations. The level density parameters of Ni63 and Co60 have been obtained from the particle evaporation spectra. We also find contributions from the break up of the lithium projectiles to the low energy region of the α spectra.

Negative electrodes for lithium cells and batteries

DOEpatents

Vaughey, John T.; Fransson, Linda M.; Thackeray, Michael M.

2005-02-15

A negative electrode is disclosed for a non-aqueous electrochemical cell. The electrode has an intermetallic compound as its basic structural unit with the formula M.sub.2 M' in which M and M' are selected from two or more metal elements including Si, and the M.sub.2 M' structure is a Cu.sub.2 Sb-type structure. Preferably M is Cu, Mn and/or Li, and M' is Sb. Also disclosed is a non-aqueous electrochemical cell having a negative electrode of the type described, an electrolyte and a positive electrode. A plurality of cells may be arranged to form a battery.

Extrusion of electrode material by liquid injection into extruder barrel

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

Keller, David Gerard; Giovannoni, Richard Thomas; MacFadden, Kenneth Orville

An electrode sheet product is formed using an extruder having a feed throat and a downstream section by separately mixing an active electrode material and a solid polymer electrolyte composition that contains lithium salt. The active electrode material is fed into the feed throat of the extruder, while a portion of at least one fluid component of the solid polymer electrolyte composition is introduced to the downstream section. The active electrode material and the solid polymer electrolyte composition are compounded in a downstream end of the extruder. The extruded sheets, adhered to current collectors, can be formed into battery cells.

Chiral diamines. 1. Relative energies of (-)-sparteine conformers, interconversion barriers, and alkyllithium complexes

NASA Astrophysics Data System (ADS)

Wiberg, K. B.; Bailey, W. F.

2000-12-01

The structures of the four lower energy sparteine complexes were examined at several theoretical levels including B3P86/6-31G∗ and B3P86/6-311+G∗. The transition states for interconverting two pairs of conformers were determined using the synchronous transit-guided quasi-Newton procedure. Complexes with lithium hydride and propyllithium also were examined. The bidentate complexes formed from conformer 1b and propyllithium had two conformations with essentially the same energy. This may account for the low enantioselectivity observed in the reaction of alkyllithium-sparteine complexes with carbonyl compounds.

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

NASA Technical Reports Server (NTRS)

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

1971-01-01

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

Redox shuttle additives for lithium-ion batteries

DOEpatents

Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

2017-03-21

An electro lye includes a compound of Formula I or IA: where each instance of R.sup.1 is independently H, alkyl, alkoxy, alkenyl, aryl, heteroaryl, or cycloalkyl; each instance of R.sup.2 is independently H, alkyl, alkoxy, alkenyl, aryl, heteroaryl, or cycloalkyl; each instance of R.sup.3 is independently H, alkyl, alkenyl, aryl, or cycloalkyl; each instance of R.sup.4 is independently H, halogen, CN, NO.sub.2, phosphate, alkyl, alkenyl, aryl, heteroaryl, or cycloalkyl; x is 1, 2, 3, 4, or 5; y is 1 or 2; and z is 0, 1, 2, 3, or 4. ##STR00001##

A surface-analytical examination of stringer particles in aluminum-lithium-copper alloys

NASA Technical Reports Server (NTRS)

Larson, L. A.; Avalos-Borja, M.; Pizzo, P. P.

1984-01-01

A surface analytical examination of powder metallurgy processed Al-Li-Cu alloys was conducted. The oxide stringer particles often found in these alloys are characterized. Particle characterization is important to more fully understand their impact on the stress corrosion and fracture properties of the alloy. The techniques used where SIMS (Secondary Ion Mass Spectroscopy) and SAM (Scanning Auger Microscopy). The results indicate that the oxide stringer particles contain both Al and LI with relatively high Li content and the Li compounds may be associated with the stringer particles, thereby locally depleting the adjacent matrix of Li solute.

Lithium/water battery with lithium ion conducting glass-ceramics electrolyte

NASA Astrophysics Data System (ADS)

Katoh, Takashi; Inda, Yasushi; Nakajima, Kousuke; Ye, Rongbin; Baba, Mamoru

Lithium/water batteries have attracted considerable attention as high power supply devices because they use high energy density lithium metal as an anode and water as a cathode. In this study, we investigate the use of lithium/water batteries that use a glass-ceramics plate as an electrolyte. A lithium ion conducting glass-ceramics plate has no through-holes and does not exhibit moisture permeation. Such a plate has stable ionic conductivity in water. Lithium/water batteries that used a glass-ceramics plate as an electrolyte had a long and stable discharge for 50 days at room temperature when the lithium metal was prevented from coming into contact with water. Lithium/seawater batteries using a glass-ceramics plate as an electrolyte also operated well in the 10-70 °C temperature range.

Electrochemical properties of doped lithium titanate compounds and their performance in lithium rechargeable batteries

NASA Astrophysics Data System (ADS)

Shenouda, Atef Y.; Murali, K. R.

Several substituted titanates of formula Li 4- xMg xTi 5- xV xO 12 (0 ≤ x ≤ 1) were synthesized (and investigated) as anode materials in rechargeable lithium batteries. Five samples labeled as S1-S5 were calcined (fired) at 900 °C for 10 h in air, and slowly cooled to room temperature in a tube furnace. The structural properties of the synthesized products have been investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transmission infrared (FTIR). XRD explained that the crystal structures of all samples were monoclinic while S1 and S3 were hexagonal. The morphology of the crystal of S1 was spherical while the other samples were prismatic in shape. SEM investigations explained that S4 had larger grain size diameter of 15-16 μm in comparison with the other samples. S4 sample had the highest conductivity 2.452 × 10 -4 S cm -1. At a voltage plateau located at about 1.55 V (vs. Li +), S4 cell exhibited an initial specific discharge capacity of 198 mAh g -1. The results of cyclic voltammetry for Li 4- xMg xTi 5- xV xO 12 showed that the electrochemical reaction was based on Ti 4+/Ti 3+ redox couple at potential range from 1.5 to 1.7 V. There is a pair of reversible redox peaks corresponding to the process of Li + intercalation and de-intercalation in the Li-Ti-O oxides.

Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li 2Mn 4O 9

NASA Astrophysics Data System (ADS)

Palos, A. Ibarra; Anne, M.; Strobel, P.

2001-08-01

The composition Li2Mn4O9, reported as a spinel oxide containing vacancies on both tetrahedral and octahedral sites [A. de Kock et al., Mater. Res. Bull. 25, 657 (1990)], was approached using three different preparation routes: low-temperature solid state reaction (A), chemical delithiation (B), and electrochemical delithiation (C). Rietveld refinements from neutron diffraction data confirmed the double-vacancy scheme proposed previously for product A, but with more tetrahedral and fewer octahedral vacancies than in the ideal Li2Mn4O9 formula. Low-temperature solid state reactions systematically result in broad reflections. Sample B, which was obtained topotactically, exhibits much narrower reflections. But chemical analyses, thermogravimetry, and neutron diffraction show that the acid treatment introduces significant amounts of protons, resulting in a formula close to Li0.92HMn4O9. Samples A and B were cycled electrochemically in lithium cells at 3 V with better stability than LiMn2O4, probably due to their higher initial manganese oxidation state. No separate electrochemical step linked to the filling of vacancies is observed in A, whereas B gives an additional redox step ca. 200 mV above the main plateau. This feature is not observed on compounds A or C; it is reversible, and seems to be a specific property of this spinel with a low initial cell parameter (8.09 Å). Sample A2 with double cation vacancies is especially stable on cycling at 3 V, and shows a very small volume variation on lithium intercalation.

Synthesis and electrochemical sodium and lithium insertion properties of sodium titanium oxide with the tunnel type structure

NASA Astrophysics Data System (ADS)

Kataoka, Kunimitsu; Akimoto, Junji

2016-02-01

Polycrystalline sample of sodium titanium oxide Na2Ti4O9 with the tunnel-type structure was prepared by topotactic sodium extraction in air atmosphere from the as prepared Na3Ti4O9 sample. The starting Na3Ti4O9 compound was synthesized by solid state reaction at 1273 K in Ar atmosphere. The completeness of oxidation reaction from Na3Ti4O9 to Na2Ti4O9 was monitored by the change in color from dark blue to white, and was also confirmed by the Rietveld refinement using the powder X-ray diffraction data. The sodium deficient Na2Ti4O9 maintained the original Na2.08Ti4O9-type tunnel structure and had the monoclinic crystal system, space group C2/m, and the lattice parameters of a = 23.1698(3) Å, b = 2.9406(1) Å, c = 10.6038(2) Å, β = 102.422(3)°, and V = 705.57(2) Å3. The electrochemical measurements of thus obtained Na2Ti4O9 sample showed the reversible sodium insertion and extraction reactions at 1.1 V, 1.5 V, and 1.8 V vs. Na/Na+, and reversible lithium insertion and extraction reactions at around 1.4 V, 1.8 V, and 2.0 V vs. Li/Li+. The reversible capacity for the lithium cell was achieved to be 104 mAh g-1 at the 100th cycle.

Structural and electrochemical study of positive electrode materials for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Jiang, Meng

The research presented in this dissertation focuses on a combined study of the electrochemistry and the structure of positive electrode materials for Li ion batteries. Li ion batteries are one of the most advanced energy storage systems and have been the subject of numerous scientific studies in recent decades. They have been widely used for various mobile devices such as cell phones, laptop computers and power tools. They are also promising candidates as power sources for automotive applications. Although intensive research has been done to improve the performance of Li ion batteries, there are still many remaining challenges to overcome so that they can be used in a wider range of applications. In particular, cheaper and safer electrodes are required with much higher reversible capacity. The series of layered nickel manganese oxides [NixLi 1/3-2x/3Mn2/3- x/3]O2 (0 < x < 1/2) are promising alternatives for Li2CoO2, the commercial positive electrode materials in Li ion batteries, because of their lower cost and higher safety and abuse tolerance, when lithium is removed from their structure. Compounds with x<1/2, in which the total Li content is higher than transition metal content, are referred as "Li-excess" materials. The "Li2MnO3-like" region is always present in this type of materials, and the overcapacity is obtained in the first charge process, which is not reversible in the following cycles. A combined X-ray diffraction, solid state nuclear magnetic resonance and X-ray absorption spectroscopy study is performed to investigate the effect of synthetic methods on the structure, to probe the structural change of the materials during cycling and to understand the electrochemical reaction mechanism. The conversion compounds are also investigated because of their high capacities. Since the various compounds have different voltage windows, they can have potential applications as both cathodes and anodes. Solid state nuclear magnetic resonance is used to study the change in the local environment of the structure during the cycling process. Two systems are included in this work, including iron fluorides and Cu-containing materials. A comparison study has been performed on FeF3 and FeF2. Different discharge reaction mechanisms are clarified for each compound, and possible phase transitions are proposed as well. As for the Cu-containing systems, three compounds were chosen with different anions: CuS, CuO and CuF2. The reaction mechanisms are studied by 63Cu, 7Li and 19F NMR and supported by powder X-ray diffraction.

Lithium in drinking water and suicide mortality: interplay with lithium prescriptions

PubMed Central

Helbich, Marco; Leitner, Michael; Kapusta, Nestor D.

2015-01-01

Background Little is known about the effects of lithium intake through drinking water on suicide. This intake originates either from natural rock and soil elution and/or accumulation of lithium-based pharmaceuticals in ground water. Aims To examine the interplay between natural lithium in drinking water, prescribed lithium-based pharmaceuticals and suicide in Austria. Method Spatial Bayesian regressions for males, females and pooled suicide mortality rates were estimated. Results Although the expected inverse association between lithium levels in drinking water and suicide mortality was confirmed for males and for total suicide rates, the relationship for females was not significant. The models do not indicate that lithium from prescriptions, assumed to accumulate in drinking water, is related to suicide risk patterns either as an individual effect or as a moderator of lithium levels in drinking water. Gender-specific differences in risk factors and local risk hot spots are confirmed. Conclusions The findings do not support the hypotheses that lithium prescriptions have measureable protective effects on suicide or that they interact with lithium in drinking water. PMID:25953888

Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism

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

Ding, Fei; Xu, Wu; Graff, Gordon L.

Lithium metal batteries are called the “holy grail” of energy storage systems. However, lithium dendrite growth in these batteries has prevented their practical applications in the last 40 years. Here we show a novel mechanism which can fundamentally change the dendritic morphology of lithium deposition. A low concentration of the second cations (including ions of cesium, rubidium, potassium, and strontium) exhibits an effective reduction potential lower than the standard reduction potential of lithium ions when the chemical activities of these second cations are much lower than that of lithium ions. During lithium deposition, these second cations will form a self-healingmore » electrostatic shield around the initial tip of lithium whenever it is formed. This shield will repel the incoming lithium ions and force them to deposit in the smoother region of the anode so a dendrite-free film is obtained. This mechanism is effective on dendrite prevention in both lithium metal and lithium ion batteries. They may also prevent dendrite growth in other metal batteries and have transformational impact on the smooth deposition in general electrodeposition processes.« less

Synthesis of lithium nitride for neutron production target of BNCT by in situ lithium deposition and ion implantation

NASA Astrophysics Data System (ADS)

Ishiyama, S.; Baba, Y.; Fujii, R.; Nakamura, M.; Imahori, Y.

2012-12-01

To achieve high performance of BNCT (Boron Neutron Capture Therapy) device, Li3N/Li/Pd/Cu four layered Li target was designed and the structures of the synthesized four layered target were characterized by X-ray photoelectron spectroscopy. For the purpose of avoiding the radiation blistering and lithium evaporation, in situ vacuum deposition and nitridation techniques were established for in situ production and repairing maintenance of the lithium target. Following conclusions were derived: Uniform lithium layer of a few hundreds nanometer was formed on Pd/Cu multilayer surface by in situ vacuum deposition technique using metallic lithium as a source material. Lithium nitrides were formed by in situ nitridation reaction by the implantation of low-energy nitrogen ions on the deposited lithium layer surface. The chemical states of the nitridated zone were close to the stoichiometric lithium nitride, Li3N. This nitridated zone formed on surface of four layered lithium target is stable for a long time in air condition. The in situ nitridation is effective to protect lithium target from degradation by unfavorable reactions.

Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes.

PubMed

Zhang, Xue-Qiang; Chen, Xiang; Cheng, Xin-Bing; Li, Bo-Quan; Shen, Xin; Yan, Chong; Huang, Jia-Qi; Zhang, Qiang

2018-05-04

Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO 3 ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN x O y on a working lithium metal anode with dendrite-free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO 3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first-principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

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

2016-01-01

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

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

DOE PAGES

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

2016-03-18

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

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

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

Liu, Yayuan; Lin, Dingchang; Liang, Zheng

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

Lithium in sediments and brines--how, why and where to search

USGS Publications Warehouse

Vine, James D.

1975-01-01

The possibility of using lithium in batteries to power electric vehicles and as fuel for thermonuclear power has focused attention on the limited resources of lithium other than in pegmatite minerals. The Clayton Valley, Nev., subsurface lithium brine has been the major source of lithium carbonate since about 1967, but the life of this brine field is probably limited to several more decades at the present rate of production. Lithium is so highly soluble during weathering and in sedimentary environments that no lithium-rich sedimentary minerals other than clays have been identified to date. The known deposits of lithium, such as the clay mineral hectorite and the lithium-rich brines, occur in closed desert basins of the Southwest in association with nonmarine evaporites. However, the ultimate source for the lithium in these deposits may be from hydrothermal solutions. The search for previously unreported deposits of nonpegmatitic lithium should consider its probable association, not only with nonmarine evaporite minerals, but also with recent volcanic and tectonic activity, as well as with deposits of boron, beryllium, fluorine, manganese, and possibly phosphate.

Lithium in drinking water and suicide mortality: interplay with lithium prescriptions.

PubMed

Helbich, Marco; Leitner, Michael; Kapusta, Nestor D

2015-07-01

Little is known about the effects of lithium intake through drinking water on suicide. This intake originates either from natural rock and soil elution and/or accumulation of lithium-based pharmaceuticals in ground water. To examine the interplay between natural lithium in drinking water, prescribed lithium-based pharmaceuticals and suicide in Austria. Spatial Bayesian regressions for males, females and pooled suicide mortality rates were estimated. Although the expected inverse association between lithium levels in drinking water and suicide mortality was confirmed for males and for total suicide rates, the relationship for females was not significant. The models do not indicate that lithium from prescriptions, assumed to accumulate in drinking water, is related to suicide risk patterns either as an individual effect or as a moderator of lithium levels in drinking water. Gender-specific differences in risk factors and local risk hot spots are confirmed. The findings do not support the hypotheses that lithium prescriptions have measureable protective effects on suicide or that they interact with lithium in drinking water. © The Royal College of Psychiatrists 2015.

Developments in the Material Fabrication and Performance of LiMn2O4 dCld Cathode Material

DTIC Science & Technology

2016-06-13

Lithium manganese spinel; Lithium rechargeable batteries , Lithium - ion battery ...requirements. Lithium and lithium - ion battery systems are highly sought after for rechargeable applications due to their high energy density (Wh/L...further optimization, the robust LixMn2O4-dCld spinel materials will be promising active materials for future integration into lithium - ion batteries

Secondary lithium batteries for space applications

NASA Technical Reports Server (NTRS)

Carter, B.; Khanna, S. K.; Yen, S. P. S.; Shen, D.; Somoano, R. B.

1981-01-01

Secondary lithium cells which use a LiAsF6-2-Me-THF electrolyte and a TiS2 intercalatable cathode exhibit encouraging cycle life at ambient temperature. Electrochemical and surface analytical studies indicate that the electrolyte is unstable in the presence of metallic lithium, leading to the formation of a lithium passivating film composed of lithium arsenic oxyfluorides and lithium fluorsilicates. The lithium cyclability remains as the most important problem to solve. Different electrolyte solvents, such as sulfolane, exhibit promising characteristics but lead to new compatibility problems with the other cell component materials.

Lithium chloride protects retinal neurocytes from nutrient deprivation by promoting DNA non-homologous end-joining

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

Zhuang Jing; Li Fan; Liu Xuan

2009-03-13

Lithium chloride is a therapeutic agent for treatment of bipolar affective disorders. Increasing numbers of studies have indicated that lithium has neuroprotective effects. However, the molecular mechanisms underlying the actions of lithium have not been fully elucidated. This study aimed to investigate whether lithium chloride produces neuroprotective function by improving DNA repair pathway in retinal neurocyte. In vitro, the primary cultured retinal neurocytes (85.7% are MAP-2 positive cells) were treated with lithium chloride, then cultured with serum-free media to simulate the nutrient deprived state resulting from ischemic insult. The neurite outgrowth of the cultured cells increased significantly in a dose-dependentmore » manner when exposed to different levels of lithium chloride. Genomic DNA electrophoresis demonstrated greater DNA integrity of retinal neurocytes when treated with lithium chloride as compared to the control. Moreover, mRNA and protein levels of Ligase IV (involved in DNA non-homologous end-joining (NHEJ) pathway) in retinal neurocytes increased with lithium chloride. The end joining activity assay was performed to determine the role of lithium on NHEJ in the presence of extract from retinal neurocytes. The rejoining levels in retinal neurocytes treated with lithium were significantly increased as compared to the control. Furthermore, XRCC4, the Ligase IV partner, and the transcriptional factor, CREB and CTCF, were up-regulated in retinal cells after treating with 1.0 mM lithium chloride. Therefore, our data suggest that lithium chloride protects the retinal neural cells from nutrient deprivation in vitro, which may be similar to the mechanism of cell death in glaucoma. The improvement in DNA repair pathway involving in Ligase IV might have an important role in lithium neuroprotection. This study provides new insights into the neural protective mechanisms of lithium chloride.« less

Differential Antidepressant-Like Response to Lithium Treatment between Mouse Strains: Effects of Sex, Maternal Care, and Mixed Genetic Background

PubMed Central

Can, Adem; Piantadosi, Sean C.; Gould, Todd D.

2013-01-01

Background Lithium is a mood stabilizer with both antidepressant and antimanic properties, though its mechanism of action is unclear. Identifying the genetic factors that influence lithium's therapeutic actions will be an important step to assist in identifying such mechanisms. We previously reported that lithium treatment of male mice has antidepressant-like effects in the C57BL/6J strain but that such effects were absent in the BALB/cJ strain. Objectives To assess the roles of both genetic, and non-genetic factors such as sex and non-shared environmental factors that may mediate differential behavioral responses to lithium. Methods Mice were treated with lithium for ten days and then tested in the forced swim test followed by lithium discontinuation and retesting to assess effects of lithium withdrawal. We also assessed effects of sex and cross-fostering on lithium response between the C57BL/6J and BALB/cJ strains, and antidepressant-like effects of lithium in the hybrid CB6F1/J strain that is derived from C57BL/6J and BALB/cJ parental strains. Results Neither sex nor maternal care significantly influenced the differential antidepressant-like profile of lithium. Withdrawal from lithium treatment reversed antidepressant-like effects in the C57BL/6J strain, but had no effects in BALB/cJ mice. Lithium treatment did not result in antidepressant-like effects in the CB6F1/J strain. Conclusions Genetic factors are likely primarily responsible for differential antidepressant-like effects of lithium in the C57BL/6J and BALB/cJ strains. Future studies identifying such genetic factors may help to elucidate the neurobiological mechanisms of lithium's therapeutic actions. PMID:23503701

Investigation of lithium distribution in the rat brain ex vivo using lithium-7 magnetic resonance spectroscopy and imaging at 17.2 T.

PubMed

Stout, Jacques; Hanak, Anne-Sophie; Chevillard, Lucie; Djemaï, Boucif; Risède, Patricia; Giacomini, Eric; Poupon, Joël; Barrière, David André; Bellivier, Frank; Mégarbane, Bruno; Boumezbeur, Fawzi

2017-11-01

Lithium is the first-line mood stabilizer for the treatment of patients with bipolar disorder. However, its mechanisms of action and transport across the blood-brain barrier remain poorly understood. The contribution of lithium-7 magnetic resonance imaging ( 7 Li MRI) to investigate brain lithium distribution remains limited because of the modest sensitivity of the lithium nucleus and the expected low brain concentrations in humans and animal models. Therefore, we decided to image lithium distribution in the rat brain ex vivo using a turbo-spin-echo imaging sequence at 17.2 T. The estimation of lithium concentrations was performed using a phantom replacement approach accounting for B 1 inhomogeneities and differential T 1 and T 2 weighting. Our MRI-derived lithium concentrations were validated by comparison with inductively coupled plasma-mass spectrometry (ICP-MS) measurements ([Li] MRI  = 1.18[Li] MS , R = 0.95). Overall, a sensitivity of 0.03 mmol/L was achieved for a spatial resolution of 16 μL. Lithium distribution was uneven throughout the brain (normalized lithium content ranged from 0.4 to 1.4) and was mostly symmetrical, with consistently lower concentrations in the metencephalon (cerebellum and brainstem) and higher concentrations in the cortex. Interestingly, low lithium concentrations were also observed close to the lateral ventricles. The average brain-to-plasma lithium ratio was 0.34 ± 0.04, ranging from 0.29 to 0.39. Brain lithium concentrations were reasonably correlated with plasma lithium concentrations, with Pearson correlation factors ranging from 0.63 to 0.90. Copyright © 2017 John Wiley & Sons, Ltd.

The influence of the push-pull effect and a π-conjugated system in conversion efficiency of bis-chalcone compounds in a dye sensitized solar cell

NASA Astrophysics Data System (ADS)

Teo, Kien Yung; Tiong, Mee Hing; Wee, Hung Yee; Jasin, Nornadia; Liu, Zhi-Qiang; Shiu, Ming Yang; Tang, Jyun Yang; Tsai, Jenn-Kai; Rahamathullah, Rafizah; Khairul, Wan M.; Tay, Meng Guan

2017-09-01

Chalcone and its related compounds are known to be π-conjugated compounds, which can be potentially used in different electronic areas include dye sensitized solar cell (DSSC). A total of six bis-chalcone compounds (1-6) have been synthesized using a Claisen-Schmidt condensation method under basic conditions. The compounds were used as the dye in DSSC to test their solar conversion efficiency. In the process of solar cell fabrication, titanium(II) oxide (TiO2) coated glass was used as the working electrode, whereas the mixture of iodine (I2), lithium iodide (LiI), 4-tertbutylpyridine (4-TBP) and 1,2-dimethyl-3-propylimidazolium (DMPII) in 3-methoxypropionitrile were used as the electrolyte. The DSSC was fabricated by immersing the TiO2 glass into the respective bis-chalcone compound solution and dried into the oven at 45 °C for 120 min. Lastly, the working electrode and counter electrode were sealed using surlyn of 60 μm thickness. The efficiency test was conducted under AM 1.5G illumination with the incident light intensity of 100 mW/cm2. Among the six bis-chalcone derivatives, compound 2, namely 1,4-bis-2-hydroxychalcone, was recorded with the highest efficiency (0.054%) compared to the others (0.022-0.035%). The presence of a π-conjugated system and the push-pull effect in the molecule were found to enhance the conversion efficiency of DSSC. Details of the results are discussed in the present paper.

Method for hot pressing beryllium oxide articles

DOEpatents

Ballard, Ambrose H.; Godfrey, Jr., Thomas G.; Mowery, Erb H.

1988-01-01

The hot pressing of beryllium oxide powder into high density compacts with little or no density gradients is achieved by employing a homogeneous blend of beryllium oxide powder with a lithium oxide sintering agent. The lithium oxide sintering agent is uniformly dispersed throughout the beryllium oxide powder by mixing lithium hydroxide in an aqueous solution with beryllium oxide powder. The lithium hydroxide is converted in situ to lithium carbonate by contacting or flooding the beryllium oxide-lithium hydroxide blend with a stream of carbon dioxide. The lithium carbonate is converted to lithium oxide while remaining fixed to the beryllium oxide particles during the hot pressing step to assure uniform density throughout the compact.

Do not treat the numbers: lithium toxicity.

PubMed

Foulser, Peter; Abbasi, Yasmin; Mathilakath, Anand; Nilforooshan, Ramin

2017-06-02

We describe the case of a 62-year-old man with a history of bipolar disorder, previously stable on lithium for over 20 years, who presented with a manic relapse and signs of lithium toxicity in the form of a coarse tremor. Serum lithium levels were in the normal range, and the patient had stage 3 chronic kidney disease. He was admitted for treatment under Section 2 of the Mental Health Act, and after stopping lithium was started on olanzapine. Signs of lithium toxicity improved after withdrawal of lithium. This case highlights the need to treat normal serum lithium levels with caution in patients showing signs of clinical lithium toxicity. © BMJ Publishing Group Ltd (unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Lithium

USGS Publications Warehouse

Bradley, Dwight C.; Stillings, Lisa L.; Jaskula, Brian W.; Munk, LeeAnn; McCauley, Andrew D.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Lithium, the lightest of all metals, is used in air treatment, batteries, ceramics, glass, metallurgy, pharmaceuticals, and polymers. Rechargeable lithium-ion batteries are particularly important in efforts to reduce global warming because they make it possible to power cars and trucks from renewable sources of energy (for example, hydroelectric, solar, or wind) instead of by burning fossil fuels. Today, lithium is extracted from brines that are pumped from beneath arid sedimentary basins and extracted from granitic pegmatite ores. The leading producer of lithium from brine is Chile, and the leading producer of lithium from pegmatites is Australia. Other potential sources of lithium include clays, geothermal brines, oilfield brines, and zeolites. Worldwide resources of lithium are estimated to be more than 39 million metric tons, which is enough to meet projected demand to the year 2100. The United States is not a major producer at present but has significant lithium resources.

Lithium metal for x-ray filters and refractive optics

NASA Astrophysics Data System (ADS)

Pereira, N. R.; Dufresne, Eric; Dierker, Steve

2001-04-01

Lithium is the most x-ray transparent solid element. Lithium is very stable in dry air with a dew point below -50 C or so, but as the humidity increases lithium starts to react with the air's nitrogen and oxygen. Under usual laboratory conditions a shiny piece of lithium metal becomes a white powder within the hour, preventing lithium's widespread use in x-ray work. Use of lithium as a window for pulsed x-rays demands that lithium withstands corrosion in open air for at least 15 minutes. Protection by a one micron layer of parylene turns out to be enough. Although parylene absorbs soft x-rays 12 times more than lithium, the parylene layer can remain in place for the window application. Lithium is also ideal for refractive x-ray lenses. We are evaluating the performance of such lenses with 10 keV photons from the MHATT-CAT beam line at the Advanced Photon Source. These measurements are in progress: the paper will show the results from these measurements as available.

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.

High rate and stable cycling of lithium metal anode

PubMed Central

Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu; Bhattacharya, Priyanka; Engelhard, Mark; Borodin, Oleg; Zhang, Ji-Guang

2015-01-01

Lithium metal is an ideal battery anode. However, dendrite growth and limited Coulombic efficiency during cycling have prevented its practical application in rechargeable batteries. Herein, we report that the use of highly concentrated electrolytes composed of ether solvents and the lithium bis(fluorosulfonyl)imide salt enables the high-rate cycling of a lithium metal anode at high Coulombic efficiency (up to 99.1%) without dendrite growth. With 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane as the electrolyte, a lithium|lithium cell can be cycled at 10 mA cm−2 for more than 6,000 cycles, and a copper|lithium cell can be cycled at 4 mA cm−2 for more than 1,000 cycles with an average Coulombic efficiency of 98.4%. These excellent performances can be attributed to the increased solvent coordination and increased availability of lithium ion concentration in the electrolyte. Further development of this electrolyte may enable practical applications for lithium metal anode in rechargeable batteries. PMID:25698340

Nanostructuring one-dimensional and amorphous lithium peroxide for high round-trip efficiency in lithium-oxygen batteries.

PubMed

Dutta, Arghya; Wong, Raymond A; Park, Woonghyeon; Yamanaka, Keisuke; Ohta, Toshiaki; Jung, Yousung; Byon, Hye Ryung

2018-02-14

The major challenge facing lithium-oxygen batteries is the insulating and bulk lithium peroxide discharge product, which causes sluggish decomposition and increasing overpotential during recharge. Here, we demonstrate an improved round-trip efficiency of ~80% by means of a mesoporous carbon electrode, which directs the growth of one-dimensional and amorphous lithium peroxide. Morphologically, the one-dimensional nanostructures with small volume and high surface show improved charge transport and promote delithiation (lithium ion dissolution) during recharge and thus plays a critical role in the facile decomposition of lithium peroxide. Thermodynamically, density functional calculations reveal that disordered geometric arrangements of the surface atoms in the amorphous structure lead to weaker binding of the key reaction intermediate lithium superoxide, yielding smaller oxygen reduction and evolution overpotentials compared to the crystalline surface. This study suggests a strategy to enhance the decomposition rate of lithium peroxide by exploiting the size and shape of one-dimensional nanostructured lithium peroxide.

Novel, Solvent Free, Single Ion Conductive Polymer Electrolytes (Warsaw-2001)

DTIC Science & Technology

2004-10-18

application in lithium and lithium - ion batteries , characterized by limited participation of anions in the transport of electrical charge. Studies...with studies on novel chemical energy conversion and storage devices mainly lithium or lithium ion batteries and fuel cells [1]. Our work within...this part of the project dealt with these novel ideas in the field of lithium or lithium - ion batteries based on polymeric solid electrolytes. The solid

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

Operando lithium plating quantification and early detection of a commercial LiFePO4 cell cycled under dynamic driving schedule

NASA Astrophysics Data System (ADS)

Anseán, D.; Dubarry, M.; Devie, A.; Liaw, B. Y.; García, V. M.; Viera, J. C.; González, M.

2017-07-01

Lithium plating is considered one of the most detrimental phenomenon in lithium ion batteries (LIBs), as it increases cell degradation and might lead to safety issues. Plating induced LIB failure presents a major concern for emerging applications in transportation and electrical energy storage. Hence, the necessity to operando monitor, detect and analyze lithium plating becomes critical for safe and reliable usage of LIB systems. Here, we report in situ lithium plating analyses for a commercial graphite||LiFePO4 cell cycled under dynamic stress test (DST) driving schedule. We designed a framework based on incremental capacity (IC) analysis and mechanistic model simulations to quantify degradation modes, relate their effects to lithium plating occurrence and assess cell degradation. The results show that lithium plating was induced by large loss of active material on the negative electrode that eventually led the electrode to over-lithiate. Moreover, when lithium plating emerged, we quantified that the loss of lithium inventory pace was increased by a factor of four. This study illustrates the benefits of the proposed framework to improve lithium plating analysis. It also discloses the symptoms of lithium plating formation, which prove valuable for novel, online strategies on early lithium plating detection.

A chemically stable PVD multilayer encapsulation for lithium microbatteries

NASA Astrophysics Data System (ADS)

Ribeiro, J. F.; Sousa, R.; Cunha, D. J.; Vieira, E. M. F.; Silva, M. M.; Dupont, L.; Goncalves, L. M.

2015-10-01

A multilayer physical vapour deposition (PVD) thin-film encapsulation method for lithium microbatteries is presented. Lithium microbatteries with a lithium cobalt oxide (LiCoO2) cathode, a lithium phosphorous oxynitride (LiPON) electrolyte and a metallic lithium anode are under development, using PVD deposition techniques. Metallic lithium film is still the most common anode on this battery technology; however, it presents a huge challenge in terms of material encapsulation (lithium reacts with almost any materials deposited on top and almost instantly begins oxidizing in contact with atmosphere). To prove the encapsulation concept and perform all the experiments, lithium films were deposited by thermal evaporation technique on top of a glass substrate, with previously patterned Al/Ti contacts. Three distinct materials, in a multilayer combination, were tested to prevent lithium from reacting with protection materials and atmosphere. These multilayer films were deposited by RF sputtering and were composed of lithium phosphorous oxide (LiPO), LiPON and silicon nitride (Si3N4). To complete the long-term encapsulation after breaking the vacuum, an epoxy was applied on top of the PVD multilayer. In order to evaluate oxidation state of lithium films, the lithium resistance was measured in a four probe setup (cancelling wires/contact resistances) and resistivity calculated, considering physical dimensions. A lithium resistivity of 0.16 Ω μm was maintained for more than a week. This PVD multilayer exonerates the use of chemical vapour deposition (CVD), glove-box chambers and sample manipulation between them, significantly reducing the fabrication cost, since battery and its encapsulation are fabricated in the same PVD chamber.

76 FR 55799 - Outbound International Mailings of Lithium Batteries

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-09

... equipment with lithium metal or lithium-ion batteries that were to be effective October 3, 2011. These... POSTAL SERVICE 39 CFR Part 20 Outbound International Mailings of Lithium Batteries AGENCY: Postal... would incorporate new maximum limits for the outbound mailing of lithium batteries to international, or...

78 FR 19024 - Lithium Ion Batteries in Transportation Public Forum

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-28

... NATIONAL TRANSPORTATION SAFETY BOARD Lithium Ion Batteries in Transportation Public Forum On... forum titled, ``Lithium Ion Batteries in Transportation.'' The forum will begin at 9:00 a.m. on both... battery design, development, and use; Lithium ion battery regulations and standards; and Lithium ion...

Spectroscopic characteristic (FT-IR, FT-Raman, UV, 1H and 13C NMR), theoretical calculations and biological activity of alkali metal homovanillates

NASA Astrophysics Data System (ADS)

Samsonowicz, M.; Kowczyk-Sadowy, M.; Piekut, J.; Regulska, E.; Lewandowski, W.

2016-04-01

The structural and vibrational properties of lithium, sodium, potassium, rubidium and cesium homovanillates were investigated in this paper. Supplementary molecular spectroscopic methods such as: FT-IR, FT-Raman in the solid phase, UV and NMR were applied. The geometrical parameters and energies were obtained from density functional theory (DFT) B3LYP method with 6-311++G** basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned. Geometric and magnetic aromaticity indices, atomic charges, dipole moments, HOMO and LUMO energies were also calculated. The microbial activity of investigated compounds was tested against Bacillus subtilis (BS), Pseudomonas aeruginosa (PA), Escherichia coli (EC), Staphylococcus aureus (SA) and Candida albicans (CA). The relationship between the molecular structure of tested compounds and their antimicrobial activity was studied. The principal component analysis (PCA) was applied in order to attempt to distinguish the biological activities of these compounds according to selected band wavenumbers. Obtained data show that the FT-IR spectra can be a rapid and reliable analytical tool and a good source of information for the quantitative analysis of the relationship between the molecular structure of the compound and its biological activity.

Electrical, dielectric properties and study of AC electrical conduction mechanism of Li0.9□0.1NiV0.5P0.5O4

NASA Astrophysics Data System (ADS)

Rahal, A.; Borchani, S. Megdiche; Guidara, K.; Megdiche, M.

2018-02-01

In this paper, we report the measurements of impedance spectroscopy for a new olivine-type lithium deficiency Li0.9□0.1NiV0.5P0.5O4 compound. It was synthesized by the conventional solid-state technique. All the X-ray diffraction peaks of the compound are indexed, and it is found that the sample is well crystallized in orthorhombic olivine structure belonging to the space group Pnma. Conductivity and dielectric analyses of the sample are carried out at different temperatures and frequencies using the complex impedance spectroscopy technique. The electrical conductivity of Li0.9□0.1NiV0.5P0.5O4 is higher than that of parent compound LiNiV0.5P0.5O4. Temperature dependence of the DC conductivity and modulus was found to obey the Arrhenius law. The obtained values of activation energy are different which confirms that transport in the title compound is not due to a simple hopping mechanism. To determine the conduction mechanism, the AC conductivity and its frequency exponent have been analysed in this work by a theoretical model based on quantum mechanical tunnelling: the non-overlapping small polaron tunnelling model.

78 FR 69516 - In The Matter of: Sovereign Lithium, Inc.; Order of Suspension of Trading

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-19

... SECURITIES AND EXCHANGE COMMISSION [File No. 500-1] In The Matter of: Sovereign Lithium, Inc... securities of Sovereign Lithium, Inc. (``Sovereign Lithium'') because of concerns regarding the accuracy and adequacy of information in the marketplace and potentially manipulative transactions in Sovereign Lithium's...

49 CFR 175.10 - Exceptions for passengers, crewmembers, and air operators.

Code of Federal Regulations, 2010 CFR

2010-10-01

... lithium metal battery, a lithium content of not more than 2 grams per battery; or (ii) For a lithium-ion... 7 (radioactive) material or lithium batteries; and radiopharmaceuticals that have been injected or... notebook computers, camcorders, etc.) containing cells or batteries (including lithium cells or batteries...

Evaluation of TIAX High Energy CAM-7/Graphite Lithium-Ion Batteries at High and Low Temperatures

DTIC Science & Technology

2014-08-01

phosphate ( LiFePO4 or LFP), lithium nickel cobalt manganese oxide (LiNixCoyMnzO2 or NCM), LCO, and NCA, CAM-7 based 18650 cells have a higher specific...electric vehicles HT high temperature Li lithium LiCoO2 or LCO lithium cobalt oxide LiCoPO4 or LCP lithium cobalt phosphate LiFePO4 or LFP lithium

Thin-film Rechargeable Lithium Batteries

DOE R&D Accomplishments Database

Dudney, N. J.; Bates, J. B.; Lubben, D.

1995-06-01

Thin film rechargeable lithium batteries using ceramic electrolyte and cathode materials have been fabricated by physical deposition techniques. The lithium phosphorous oxynitride electrolyte has exceptional electrochemical stability and a good lithium conductivity. The lithium insertion reaction of several different intercalation materials, amorphous V{sub 2}O{sub 5}, amorphous LiMn{sub 2}O{sub 4}, and crystalline LiMn{sub 2}O{sub 4} films, have been investigated using the completed cathode/electrolyte/lithium thin film battery.

Facile Synthesis of Pre-Doping Lithium-Ion Into Nitrogen-Doped Graphite Negative Electrode for Lithium-Ion Capacitor.

PubMed

Lee, Seul-Yi; Kim, Ji-Il; Rhee, Kyong Yop; Park, Soo-Jin

2015-09-01

Nitrogen-doped graphite, prepared via the thermal decomposition of melamine into a carbon matrix for use as the negative electrode in lithium-ion capacitors (LICs), was evaluated by electrochemical measurements. Furthermore, in order to study the performance of pre-doped lithium components as a function of nitrogen-doped material, the pre-doped lithium graphite was allowed to react with a lithium salt solution. The results showed that the nitrogen functional groups in the graphite largely influenced the pre-doped lithium components, thereby contributing to the discharge capacity and cycling performance. We confirmed that the large initial irreversible capacity could be significantly decreased by using pre-doped lithium components obtained through the nitrogen-doping method.

Chemical and morphological characteristics of lithium electrode surfaces

NASA Technical Reports Server (NTRS)

Yen, S. P. S.; Shen, D.; Vasquez, R. P.; Grunthaner, F. J.; Somoano, R. B.

1981-01-01

Lithium electrode surfaces were analyzed for chemical and morphological characteristics, using electron spectroscopy chemical analysis (ESCA) and scanning electron microscopy (SEM). Samples included lithium metal and lithium electrodes which were cycled in a 1.5 M lithium arsenic hexafluoride/two-methyl tetrahydrofuran electrolyte. Results show that the surface of the as-received lithium metal was already covered by a film composed of LiO2 and an Li2O/CO2 adduct with a thickness of approximately 100-200 A. No evidence of Ni3 was found. Upon exposure of the lithium electrode to a 1.5 M LiAsF6/2-Me-THF electrochemical environment, a second film was observed to form on the surface, consisting primarily of As, Si, and F, possibly in the form of lithium arsenic oxyfluorides or lithium fluorosilicates. It is suggested that the film formation may be attributed to salt degradation.

Proton enhanced dynamic battery chemistry for aprotic lithium-oxygen batteries.

PubMed

Zhu, Yun Guang; Liu, Qi; Rong, Yangchun; Chen, Haomin; Yang, Jing; Jia, Chuankun; Yu, Li-Juan; Karton, Amir; Ren, Yang; Xu, Xiaoxiong; Adams, Stefan; Wang, Qing

2017-02-06

Water contamination is generally considered to be detrimental to the performance of aprotic lithium-air batteries, whereas this view is challenged by recent contrasting observations. This has provoked a range of discussions on the role of water and its impact on batteries. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic lithium-oxygen batteries is revealed. Both lithium ions and protons are found to be involved in the oxygen reduction and evolution reactions, and lithium hydroperoxide and lithium hydroxide are identified as predominant discharge products. The crystallographic and spectroscopic characteristics of lithium hydroperoxide monohydrate are scrutinized both experimentally and theoretically. Intriguingly, the reaction of lithium hydroperoxide with triiodide exhibits a faster kinetics, which enables a considerably lower overpotential during the charging process. The battery chemistry unveiled in this mechanistic study could provide important insights into the understanding of nominally aprotic lithium-oxygen batteries and help to tackle the critical issues confronted.

Lithium: for harnessing renewable energy

USGS Publications Warehouse

Bradley, Dwight; Jaskula, Brian W.

2014-01-01

Lithium, which has the chemical symbol Li and an atomic number of 3, is the first metal in the periodic table. Lithium has many uses, the most prominent being in batteries for cell phones, laptops, and electric and hybrid vehicles. Worldwide sources of lithium are broken down by ore-deposit type as follows: closed-basin brines, 58%; pegmatites and related granites, 26%; lithium-enriched clays, 7%; oilfield brines, 3%; geothermal brines, 3%; and lithium-enriched zeolites, 3% (2013 statistics). There are over 39 million tons of lithium resources worldwide. Of this resource, the USGS estimates there to be approximately 13 million tons of current economically recoverable lithium reserves. To help predict where future lithium supplies might be located, USGS scientists study how and where identified resources are concentrated in the Earth’s crust, and they use that knowledge to assess the likelihood that undiscovered resources also exist.

Lithium Recovery from Aqueous Resources and Batteries: A Brief Review

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

Li, Ling; Deshmane, Vishwanath G.; Paranthaman, M. Parans

The demand for lithium is expected to increase drastically in the near future due to the increased usage of rechargeable lithium-ion batteries (LIB) in electric vehicles, smartphones and other portable electronics. To alleviate the potential risk of undersupply, lithium can be extracted from raw sources consisting of minerals and brines or from recycled batteries and glasses. Aqueous lithium mining from naturally occurring brines and salt deposits is advantageous compared to extraction from minerals, since it may be more environmentally friendly and cost-effective. In this article, we briefly discuss the adsorptive behaviour, synthetic methodology and prospects or challenges of major sorbentsmore » including spinel lithium manganese oxide (Li-Mn-O or LMO), spinel lithium titanium oxide (Li-Ti-O or LTO) and lithium aluminium layered double hydroxide chloride (LiCl·2Al(OH)3). Membrane approaches and lithium recovery from end-of-life LIB will also be briefly discussed.« less

Lithium Recovery from Aqueous Resources and Batteries: A Brief Review

DOE PAGES

Li, Ling; Deshmane, Vishwanath G.; Paranthaman, M. Parans; ...

2018-04-01

The demand for lithium is expected to increase drastically in the near future due to the increased usage of rechargeable lithium-ion batteries (LIB) in electric vehicles, smartphones and other portable electronics. To alleviate the potential risk of undersupply, lithium can be extracted from raw sources consisting of minerals and brines or from recycled batteries and glasses. Aqueous lithium mining from naturally occurring brines and salt deposits is advantageous compared to extraction from minerals, since it may be more environmentally friendly and cost-effective. In this article, we briefly discuss the adsorptive behaviour, synthetic methodology and prospects or challenges of major sorbentsmore » including spinel lithium manganese oxide (Li-Mn-O or LMO), spinel lithium titanium oxide (Li-Ti-O or LTO) and lithium aluminium layered double hydroxide chloride (LiCl·2Al(OH)3). Membrane approaches and lithium recovery from end-of-life LIB will also be briefly discussed.« less

Comparative Study of Ether-Based Electrolytes for Application in Lithium-Sulfur Battery.

PubMed

Carbone, Lorenzo; Gobet, Mallory; Peng, Jing; Devany, Matthew; Scrosati, Bruno; Greenbaum, Steve; Hassoun, Jusef

2015-07-01

Herein, we report the characteristics of electrolytes using various ether-solvents with molecular composition CH3O[CH2CH2O]nCH3, differing by chain length, and LiCF3SO3 as the lithium salt. The electrolytes, considered as suitable media for lithium-sulfur batteries, are characterized in terms of thermal properties (TGA, DSC), lithium ion conductivity, lithium interface stability, cyclic voltammetry, self-diffusion properties of the various components, and lithium transference number measured by NMR. Furthermore, the electrolytes are characterized in lithium cells using a sulfur-carbon composite cathode by galvanostatic charge-discharge tests. The results clearly evidence the influence of the solvent chain length on the species mobility within the electrolytes that directly affects the behavior in lithium sulfur cell. The results may effectively contribute to the progress of an efficient, high-energy lithium-sulfur battery.

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.