Alloy formation processes at electrochemical intercalation of lithium into intermetallic compounds of magnesium with zinc

A comparative study of alloy formation processes that occur during the electrochemical intercalation of lithium from lithium chloride solutions in dimethylformamide into intermetallic compounds of magnesium with zinc (MgZn₂, Mg₂Zn₃) and the corresponding individual metals is studied by chronopotentiometric and voltammetric methods. Lithium-containing phases are formed in all samples studied; moreover, for MgZn₂ and Mg₂Zn₃ electrodes, the phases formed are preferentially in the Li-Zn system. The largest number of lithium-containing phases is formed in zinc. It is shown that the electrochemical behavior of intermetallic electrodes is associated with their nature, where a single alloy component plays the key role, namely, zinc for MgZn₂ and magnesium for Mg₂Zn₃. The cathodic intercalation of lithium into MgZn₂ is characterized by anomalously low polarizability as compared with the other electrodes. The lithium extraction coefficient K _ex ^Li increases from the first to the tenth cycle for all electrode studied. The highest K _ex ^Li are typical of Zn and the lowest are typical of Mg₂Zn₃.     

Phase Formation and Kinetics of Electrochemical Intercalation of Lithium into Intermetallic Compounds MgCd and MgCd3

Electrochemical intercalation of lithium into intermetallic compounds (IMC) MgCd and MgCd₃ out of propylene carbonate solutions of LiBF₄ is studied. According to chronopotentiometry data, during the intercalation, lithium forms compounds with cadmium: Li₃Cd on MgCd or LiCd and Li₃Cd on MgCd₃. Reactions of solid-phase substitution, which occur on the electrodes, are accompanied by the destruction of initial IMC and generation of magnesium atoms. Chronoamperometry of MgCd–(Li) and MgCd₃–(Li) shows the lithium intercalation to be limited by nonstationary diffusion of lithium in the solid phase. The lithium diffusion in MgCd is slower and that in MgCd₃is faster than in Cd. The calculated potential dependences of the diffusion coefficient for lithium in MgCd and MgCd₃ are linear in semilogarithmic coordinates.     

Hydrogenation of fullerites in the presence of intermetallic compounds or metals

Fullerene hydrides containing 24–26 H atoms per fullerene molecule were obtained by hydrogenation of solid-phase mixtures of fullerenes with either intermetallic compounds LaNi₅, LaNi_4.65Mn_0.35, CeCo₃ or V and Pd metals with gaseous hydrogen at 1.0–2.5 MPa and 573–673 K. These fullerene hydrides decompose at 800 K with evolution of H₂. Upon subsequent heating to 1000 K, vanadium reacts with fullerene to yield a cubic phase of vanadium carbide. The intermetallic compounds react with fullerene with the formation of a metallic phase of the 3d-metal and destruction of fullerene. Palladium does not react with fullerene. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 679–683, April, 1997.     

The metal flux: a preparative tool for the exploration of intermetallic compounds

This review highlights the use and great potential of liquid metals as exotic and powerful solvents (i.e. fluxes) for the synthesis of intermetallic phases. The results presented demonstrate that considerable advances in the discovery of novel and complex phases are achievable utilizing molten metals as solvents. A wide cross-section of examples of flux-grown intermetallic phases and related solids are discussed and a brief history of the origins of flux chemistry is given. The most commonly used metal fluxes are surveyed and where possible, the underlying principal reasons that make the flux reaction work are discussed.     

Hydrides of intermetallic compounds with a H/M ratio greater than unity obtained at high hydrogen pressures

Novel hydride phases with H/M > 1 based on Zr₂Pd, Hf₂Pd, and Hf₂Cu (structures of the MoSi₂, type) have been synthesized at high H₂ pressures. The X-ray diffraction investigations of the resulting hydrides have been carried out. Some factors determining the maximum hydrogen content in the hydrides of intermetallic compounds are discussed. A model structure of the hydrides obtained is proposed, which assumes the possibility of direct H-H interactions when the interatomic distances are less than 1 Å.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 843–845, May, 1993.     

Metalation of 1-R-2-benzyl-o-carboranes with lithium aluminum hydride

Carboranes with the general formula I-R-2-PhCH₂-1,2-C₂B₁₀H₁₀ (R = Me, Prⁱ, Ph, PhCH₂) are readily metalated with lithium aluminum hydride in a THF solution at the CH₂ group. In this case only one hydrogen atom in LiAlH₄ is substituted, and trihydride complexes 1-R-2-PhCH(AlH₃Li)-1,2-C₂B₁₀H₁₀, are formed, which are stable in a solutionTranslated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1282–1284, May, 1996.     

Characterisation of four new two-dimensional lithium beryllofluoro-layered compounds

Four new amine-templated materials, containing two-dimensional lithium beryllofluoride sheets of the stoichiometry [LiBeF(4)](-), have been synthesised under hydrothermal and ambient pressure conditions. [LiBeF(4)][C(6)H(4)(CH(3))CH(2)NH(3)] (1), [LiBeF(4)][C(6)H(4)CH(2)NH(3)Cl] (2), [LiBeF(4)](2)[NH(3)CH(2)CH(2)CH(2)NH(3)] (3), and [LiBeF(4)][C(6)H(5)CH(2)CH(2)CH(2)NH(3)] (4) all contain well-separated anionic sheets containing two different topologies with the 'inter-layer' regions comprising of organoamine templating species. Use of the different organoamine templating agents results in compounds possessing very different relative arrangements of the lithium beryllofluoride sheets. The materials crystallise in P-centred orthorhombic and monoclinic cells; for 1 (templating agent: 3-methylbenzylamine) Pca2(1); for 2 (4-chlorobenzylamine) Pbca; for 3 (1,3-diamminopropane) Pccn, and for 4 (3-phenyl-1-propylamine) P2(1)/c. Hydrogen bonding exists between ions situated on the protonated amine groups on the templating species and electronegative fluoride ions, on MF(4) tetrahedra (where M=Li and Be).     

Dynamics of lithium electrode passivation in aprotic organic electrolytes,studied by electrochemical noise method

Lithium electrode passivation is studied in different organic electrolytes, namely, 1 M LiClO₄ in 1,3-dioxolane, 1 M LiN(CF₃SO₂)₂ in 1,3-dioxolane, 1 M LiPF₆ in an ethylene carbonate-diethyl carbonate mixture, 1 M LiPF₆ in an ethylene carbonate-dimethyl carbonate mixture, using the electrochemical noise method. The dynamics of passive film formation on the lithium surface in the mentioned electrolytes that differ in their corrosivity towards lithium is followed.     

Phase transformations in hydrogen sorption-desorption by hydrides of intermetallic compounds of the CrB structural type

State Institute of the Nitrogen Industry. M. V. Lomonosov State University, Moscow. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 5, pp. 74–81, September–October, 1991.     

Physicochemical and electrochemical properties of sulfolane solutions of lithium salts

The physicochemical and electrochemical properties (electrical conductivity, viscosity, density, and electrochemical stability) of sulfolane solutions of various lithium salts are studied. The nature of the anion considerably affects the physicochemical and electrochemical properties of the electrolyte systems considered. Sulfolane solutions of lithium salts have moderate electrical conductivity and high electrochemical stability, and can be used as electrolytes in lithium batteries.     

Valence state of hydrogen in hydrides of intermetallic compounds

The experimental data on the mechanism of hydride dispersion of intermetallic compounds of the LaNi₅ type and the crystal structures of hydride phases based on these compounds were analyzed. A new approach was suggested and substantiated, which allows one to consider hydride dispersion as a result of a redox process associated with the formation of H^δ− hydride ions at concentrations of hydrogen in the solid hydrideC _H>-C _{H cr}. The value ofC _{H cr} is determined by the redox potential of the reaction H^δ++M^δ−⇌H^δ′−+M^δ′+. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 214–217, February, 1998.     

Synthesis of carbon nanofibers by catalytic pyrolysis of ethylene and methane on hydrides of intermetallic compounds of lanthanum with nickel

Carbon nanofibers were synthesized by the pyrolysis of ethylene and methane on hydrides of intermetallides LaNi_nH_x (n = 2, 3, 5; x = 0.1–4). The influence of parameters of the synthesis (temperature and the ratio of gases in an Ar: H₂: C₂H₄ (CH₄) mixture) on the structure of nanofibers thus formed was studied. Hydrides of nickel intermetallides are more efficient catalytic systems than metallic nickel. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2210–2214, October, 2005.     

Effective extractants for the extraction of lithium from aqueous solutions containing sodium and potassium compounds

The extraction power of newly obtained pure methoxy-1,3-diketones in diluents and in their mixtures with electron-donating additives during the extraction of lithium from aqueous solutions containing sodium and potassium was investigated. High separation factors were obtained; no appreciable amounts of sodium and potassium were found in the extract after total extraction of the lithium.Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1304–1310, June, 1992.     

Comparative study of boron compounds and aluminum trihydroxide as flame retardant additives in epoxy resin

The aim of this study was to investigate and compare the flame retardant properties of boron compounds with respect to aluminum trihydroxide (ATH) in an epoxy system based on bisphenol A epichlorohydrin‐based epoxy resin and cycloaliphatic polyamine‐based hardener. Six different boron compounds including colemanite (C), ulexite (U), boric acid (BA), boric oxide (BO), melamine borate (MB) and guanidinium nonaborate (GB) were used as flame retardant additive. The flame retardant properties of epoxy‐based composites were investigated using limiting oxygen index (LOI), UL 94 standards both in vertical and horizontal position, thermogravimetric analysis, cone calorimeter and scanning electron microscopy. According to flammability test results, boron compounds except for C and U showed better performance than ATH. According to the LOI results, 40% BA containing sample had the highest LOI value of 28.5, while 30% MB, 35% GB and 40% BA containing samples had the highest UL 94V rating (V0). According to the cone calorimeter test results, all boron containing samples had better fire performances than ATH containing sample; 40 wt% BO containing sample showed the lowest peak heat release rate, average heat release rate and total heat release values. Copyright © 2014 John Wiley & Sons, Ltd.     

Organoelement compounds in the electrochemical synthesis of fluoroorganics

Electrochemical generation of organic anion-radicals in the presence of fluoroorganosilanes causes the chain addition reaction. Adducts of CFCl₂SiMe₃, CFClCFSiMe₃ and CF₃SiMe₃ with benzaldehyde were obtained with conversion efficiency up to 8000%.Electroreduction of bis-(trifluoromethyl)mercury (II) was established to be the route for the intermediate formation of trifluoromethyl anion, which was trapped by the reactions with benzaldehyde, Me₃SiCl and bromobenzonitrile.The use of salen Ni(II) complex as mediator allows the electrochemical reduction of polyfluoroalkylchlorides at the potentials more than 1 V higher than their reduction potentials.     

金属改性与碳包覆的多孔硅微球复合材料的制备及其电化学储锂性能

以工业级SiAl合金微球为前驱物,采用多步刻蚀-热处理策略,制备了金属(Sb-Sn)改性与碳包覆的多孔硅微球复合材料(pSi/Sb-Sn@C)。pSi/Sb-Sn@C具有以 Sb-Sn改性的多孔硅微球(pSi/Sb-Sn)为核、碳包覆层为壳的三维结构。碳外壳可以提高多孔硅微球的电子导电性和机械稳定性,有利于获得稳定的固体电解质界面(SEI)膜;而三维多孔核可以促进锂离子的扩散,增加嵌/脱锂活性位,缓冲嵌锂过程中的体积膨胀。此外,活性金属(Sb-Sn)的引入能够提高复合材料的导电性,并可以贡献一定的储锂容量。由于其特殊的组成和独特的微观结构,pSi/Sb-Sn@C复合材料在1.0 A·g^-1电流密度下充放电300次后的可逆容量为1 247.4 mAh·g^-1,显示了良好的高速率储锂性能和优异的电化学嵌/脱锂循环稳定性。     

Electrochemical Phase Evolution of Metal-Based Pre-Catalysts for High-Rate Polysulfide Conversion

In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li-S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal-based pre-catalysts (Co₄N) in working Li-S batteries that renders highly active electrocatalysts (CoS_x). Electrochemical cycling induces the transformation from single-crystalline Co₄N to polycrystalline CoS_x that are rich in active sites. This transformation propels all-phase polysulfide-involving reactions. Consequently, Co₄N enables stable operation of high-rate (10 C, 16.7 mA cm⁻²) and electrolyte-starved (4.7 μL mg_S⁻¹) Li-S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low-valence metal compounds.     

锂电池电极过程的原位电化学原子力显微镜研究进展

随着人类对能源的使用与存储需求不断增加,高能量密度和高安全性能的二次锂电池体系正在被不断地开发与完善.深入理解充放电过程中锂电池内部电极/电解质界面的电化学过程以及微观反应机理,有利于指导电池材料的优化设计.原位电化学原子力显微镜将原子力显微镜的高分辨表界面分析优势与电化学反应装置相结合,能够在电池运行条件下实现对电极/电解质界面的原位可视化研究,并进一步从纳米尺度上揭示界面结构的演化规律与动力学过程.本文总结了原位电化学原子力显微镜在锂电池电极过程中的最新研究进展,主要包括基于转化型反应的正极过程、固体电解质中间相的动态演化以及固态电池界面演化与失效分析.     

Detection of nanoscale η‐MgZn2 phase dissolution from an Al‐Zn‐Mg‐Cu alloy by electrochemical microtransients

In this article we demonstrate how the dissolution of nanosize intermetallic particles present in Al alloys can be detected using microelectrochemical techniques. The local electrochemical properties of a high‐strength Al‐Zn‐Mg‐Cu alloy, which contains nanoscale η‐MgZn₂ phases, were investigated with a microcapillary cell. At the open‐circuit potential (OCP) with the sample surface in the range of 1000 µm², potential fluctuations (microtransients) can be observed. Under polarization of such small areas, current transients are detected in the passive range of the alloy. An estimation of the size of dissolution events from the charge passed during the current transient leads to the conclusion that the current transients could stem from the dissolution of η‐phase particles, with diameters in the order of 100 nm. This size scale corresponds well with the size of the grain‐boundary MgZn₂. Transmission electron microscopy (TEM) and high‐resolution SEM images provide further insights for possible mechanisms leading either to potential or to current microtransients. Copyright © 2008 John Wiley & Sons, Ltd.