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1310-65-2Relevant academic research and scientific papers
Lithium-air and lithium-copper batteries based on a polymer stabilized interface between two immiscible electrolytic solutions (ITIES)
Wu, Borong,Chen, Xiaohui,Zhang, Cunzhong,Mu, Daobin,Wu, Feng
, p. 2140 - 2145 (2012)
We propose and demonstrate the direct application of immiscible aqueous/organic interfaces in lithium-air and lithium-copper batteries. Therefore, the two half-reactions are separated in their respectively favourable electrolytic environments without using any other membranes. In order to prevent water and oxygen from interrupting the reaction in organic phases, we add poly(methyl methacrylate) (PMMA) to propylene carbonate (PC) and investigate its concentration effects using Pt ultramicroelectrodes (UMEs). Pt UMEs provide us the sensitive measure of water contamination as well as the diffusion property of oxygen in the polymer electrolytes. By studying the discharge profiles under various electrolytic conditions, we demonstrate that these batteries are of longer discharge time and higher specific capacity when the polymer electrolyte contains about 10 to 20% of PMMA.
Mehrfachbindungen zwischen Hauptgruppenelementen und Uebergangsmetallen. LXII. Alkin-Komplexe der Organorheniumoxide: Redox-Chemie und Nucleophilie der Oxo-Funktion von (η5-Pentamethylcyclopentadienyl)(η2-diphenylethin)oxorhenium(III)
Herrmann, Wolfgang A.,Fischer, Roland A.,Amslinger, Wolfgang,Herdtweck, Eberhardt
, p. 333 - 344 (1989)
The novell ReIII oxo alkyne complexes (η5-C5Me5)Re(=O)(η2-RCCR) (3a-c; R=C6H5, CH3, C2H5) are obtained almost quantitatively by alkaline hydrolysis of the dichloro precursor compounds (η5-C5Me5)ReCl2(η2-RCCR) (4a-c).An X-ray diffraction study has revealed that in the phenyl derivative 3a the alkyne group is best described as a two-electron ligand. 17O NMR spectroscopy shows the remarkable electron deficiency of the terminal oxo group.This oxo function however is sufficiently nucleophilic to be converted into the hydroxo species 2-diphenylalkyne)hydroxo(η5-pentamethylcyclopentadienyl)rhenium(III) tetrafluoroborate (5a) and 2-butyne(2))hydroxo(η5-pentamethylcyclopentadienyl)rhenium(III)> tetrafluoroborate (5b) by O-protonation with HBF4.One-electron oxidation of 3a leads to the dinuclear ReIV species 5-C5Me5)Re(η2-C6H5CCC6H5))2>2+ without loss of the alkyne ligand.The ReV systems (η5-C5Me5)Re(=O)2(η5-RCCR) (2), generated oxidatively, are not stable as they decompose rapidly by eliminating the alkyne ligand.
Stability of lithium hydride in argon and air
Ren, Ruiming,Ortiz, Angel L.,Markmaitree, Tippawan,Osborn, William,Shaw, Leon L.
, p. 10567 - 10575 (2006)
The oxidation behaviors of LiH under a high purity argon atmosphere, an argon atmosphere with some O2 and H2O impurities, and ambient air at both room and high temperatures, are investigated using a variety of analytical instruments including X-ray diffractometry, thermogravimetry, mass spectrometry, scanning electron microscopy, and specific surface area analysis. The oxidation behaviors of the ball-milled LiH under different atmospheres are also studied and compared with those without ball milling. It is shown that no oxidation of LiH occurs under a high-purity argon atmosphere. However, oxidation of LiH takes place when the argon atmosphere contains some H2O and O2 impurities. At temperatures higher than ～55 °C, oxidation of LiH proceeds via the reaction of LiH + 1/4 O2 = 1/2 Li2O + 1/2 H2, whereas at room temperature oxidation of LiH is likely caused by the simultaneous reactions of LiH + H2O = LiOH + H2 and LiH + 1/2 O2 = LiOH. The oxidation behavior of LiH in ambient air with a 27% relative humidity can be well described by the Johnson-Mehl - Avrami equation. Furthermore, the ball-milled LiH oxidizes faster than the unmilled one, which is due to the finer particle size and larger surface area of the ball-milled powder.
The presence of water in the common CeCl3/RLi alkylation system
Evans, William J.,Feldman, Jay D.,Ziller, Joseph W.
, p. 4581 - 4584 (1996)
Dehydration of CeCl3(H2O)7 following standard procedures for making the commonly-used CeCl3/RLi reagent forms a material containing water and not anhydrous CeCl3. Heating CeCl3(H2O)7 at 150 °C and 0.03 Torr for 12 h forms a material which has an elemental composition of [CeCl3(H2O)](n), contains water by Karl Fischer analysis, reacts with MeLi to form methane, and crystallizes from THF as [Ce(μ-Cl)3(THF)(H2O)](n) in space group PI? with a = 6.691 (2) A?, b = 7.433(2) A?, c = 10.092(2) A?, α = 84.46(2)°, β = 76.72(2)°, γ = 74.76(3)°, V = 471.0(2) A?3, ρ(calcd) = 2.37 g/cm3, and Z = 2 at T = 158 K. [Ce(μ-Cl)3(THF)(H2O)](n) crystallizes in a layered structure in which eight-coordinate cerium atoms are ligated to terminal water and THF ligands and six bridging chlorides in a distorted square antiprismatic geometry. The THF ligands extend above and below the layers which contain the water molecules. Reactions of 'CeCl3/RLi' must take into account the presence of 1 equiv of water.
Thermal analysis of lithium peroxide prepared by various methods
Ferapontov,Kokoreva,Kozlova,Ul'Yanova
, p. 891 - 894 (2009)
Behavior of lithium peroxide samples at heating in air was studied by the methods of thermogravimetric analysis (TGA) and differential thermal analysis (DTA). In the temperature range from 32 to 82°C all the studied samples we found to react with water vapor forming lithium peroxide monohydrate as confirmed by the methods of chemical analysis and of qualitative X-ray phase analysis. It was found experimentally that in the temperature range from 340 to 348°C lithium peroxide began to decompose into lithium oxide and oxygen, the starting temperature depended on the method of preparation of lithium peroxide. For all the studied samples polymorphism in the temperature range from 25 to 340°C was not detected.
The standard molar enthalpies of formation of the lithium zirconates
Wyers, G. P.,Cordfunke, E. H. P.,Ouweltjes, W.
, p. 1095 - 1100 (1989)
The enthalpies of solution of Li2ZrO3, Li6Zr2O7, and Li8ZrO6 in HF*100H2O have been measured.The results have been used to derive the standard molar enthalpies of formation at 298.15 K: ΔfH0m(Li2ZrO3) = -(1742.8 +/- 1.2) k
Synthesis of the Metastable Cubic Phase of Li2OHCl by a Mechanochemical Method
Yamamoto, Takayuki,Shiba, Hinata,Mitsukuchi, Naohiro,Sugumar, Manoj Krishna,Motoyama, Munekazu,Iriyama, Yasutoshi
, p. 11901 - 11904 (2020)
The oxyhalide-based solid electrolyte Li2OHCl usually forms the thermodynamically stable orthorhombic phase at room temperature and shows poor lithium ionic conductivity. Above 35 °C, a structural phase transition into the cubic phase occurs and ionic conductivity is enhanced. In this work, mechanochemical synthesis of Li2OHCl is reported. The as-prepared Li2OHCl formed a cubic Pm3ˉ m structure and showed an ionic conductivity of 2.6 × 10-6 S cm-1 at 25 °C. Once the cubic phase was treated at 200 °C, the orthorhombic Pmc21 structure appeared at 25 °C and the ionic conductivity decreased down to 1.4 × 10-7 S cm-1. Formation of the metastable cubic phase could be explained in terms of low crystallinity of Li2OHCl derived from mechanochemical synthesis.
The Effect of Water on Quinone Redox Mediators in Nonaqueous Li-O2 Batteries
Liu, Tao,Frith, James T.,Kim, Gunwoo,Kerber, Rachel N.,Dubouis, Nicolas,Shao, Yuanlong,Liu, Zigeng,Magusin, Pieter C. M. M.,Casford, Michael T. L.,Garcia-Araez, Nuria,Grey, Clare P.
, p. 1428 - 1437 (2018)
The parasitic reactions associated with reduced oxygen species and the difficulty in achieving the high theoretical capacity have been major issues plaguing development of practical nonaqueous Li-O2 batteries. We hereby address the above issues by exploring the synergistic effect of 2,5-di-tert-butyl-1,4-benzoquinone and H2O on the oxygen chemistry in a nonaqueous Li-O2 battery. Water stabilizes the quinone monoanion and dianion, shifting the reduction potentials of the quinone and monoanion to more positive values (vs Li/Li+). When water and the quinone are used together in a (largely) nonaqueous Li-O2 battery, the cell discharge operates via a two-electron oxygen reduction reaction to form Li2O2, with the battery discharge voltage, rate, and capacity all being considerably increased and fewer side reactions being detected. Li2O2 crystals can grow up to 30 μm, more than an order of magnitude larger than cases with the quinone alone or without any additives, suggesting that water is essential to promoting a solution dominated process with the quinone on discharging. The catalytic reduction of O2 by the quinone monoanion is predominantly responsible for the attractive features mentioned above. Water stabilizes the quinone monoanion via hydrogen-bond formation and by coordination of the Li+ ions, and it also helps increase the solvation, concentration, lifetime, and diffusion length of reduced oxygen species that dictate the discharge voltage, rate, and capacity of the battery. When a redox mediator is also used to aid the charging process, a high-power, high energy density, rechargeable Li-O2 battery is obtained.
The effect of 3D carbon nanoadditives on lithium hydroxide monohydrate based composite materials for highly efficient low temperature thermochemical heat storage
Li, Shijie,Huang, Hongyu,Li, Jun,Kobayashi, Noriyuki,Osaka, Yugo,He, Zhaohong,Yuan, Haoran
, p. 8199 - 8208 (2018)
Lithium hydroxide monohydrate based thermochemical heat storage materials were modified with in situ formed 3D-nickel-carbon nanotubes (Ni-CNTs). The nanoscale (5-15 nm) LiOH·H2O particles were well dispersed in the composite formed with Ni-CNTs. These composite materials exhibited improved heat storage capacity, thermal conductivity, and hydration rate owing to hydrogen bonding between H2O and hydrophilic groups on the surface of Ni-CNTs, as concluded from combined results of in situ DRIFT spectroscopy and heat storage performance test. The introduction of 3D-carbon nanomaterials leads to a considerable decrease in the activation energy for the thermochemical reaction process. This phenomenon is probably due to Ni-CNTs providing an efficient hydrophilic reaction interface and exhibiting a surface effect on the hydration reaction. Among the thermochemical materials, Ni-CNTs-LiOH·H2O-1 showed the lowest activation energy (23.3 kJ mol-1), the highest thermal conductivity (3.78 W m-1 K-1) and the highest heat storage density (3935 kJ kg-1), which is 5.9 times higher than that of pure lithium hydroxide after the same hydration time. The heat storage density and the thermal conductivity of Ni-CNTs-LiOH·H2O are much higher than 1D MWCNTs and 2D graphene oxide modified LiOH·H2O. The selection of 3D carbon nanoadditives that formed part of the chemical heat storage materials is a very efficient way to enhance comprehensive performance of heat storage activity components.
Anti-Perovskite Li-Battery Cathode Materials
Lai, Kwing To,Antonyshyn, Iryna,Prots, Yurii,Valldor, Martin
, p. 9645 - 9649 (2017)
Through single-step solid-state reactions, a series of novel bichalcogenides with the general composition (Li2Fe)ChO (Ch = S, Se, Te) are successfully synthesized. (Li2Fe)ChO (Ch = S, Se) possess cubic anti-perovskite crystal structures, where Fe and Li are completely disordered on a common crystallographic site (3c). According to Goldschmidt calculations, Li+ and Fe2+ are too small for their common atomic position and exhibit large thermal displacements in the crystal structure models, implying high cation mobility. Both compounds (Li2Fe)ChO (Ch = S, Se) were tested as cathode materials against graphite anodes (single cells); They perform outstandingly at very high charge rates (270 mA g-1, 80 cycles) and, at a charge rate of 30 mA g-1, exhibit charge capacities of about 120 mA h g-1. Compared to highly optimized Li1-xCoO2 cathode materials, these novel anti-perovskites are easily produced at cost reductions by up to 95% and, yet, possess a relative specific charge capacity of 75%. Moreover, these iron-based anti-perovskites are comparatively friendly to the environment and (Li2Fe)ChO (Ch = S, Se) melt congruently; the latter is advantageous for manufacturing pure materials in large amounts.
