Electrochemical Behavior of Partially-Discharged Li x V2O5 Electrodes upon Interruption of Current

A mathematical diffusion model, which takes into account the electrochemical behavior of partially-discharged thin-layer electrodes made of intercalation materials upon interruption of circuit, is put forward. The applicability of the model is tested by the example of Li _x V₂O₅ films. According to theoretical calculations and experimental data, the equilibrium potential of the films studied depends practically linearly on the degree of intercalation with a slope of –0.8 V for intercalation degrees of 0.3–0.7. The chemical diffusion coefficient of lithium in the films is equal to 1.5 × 10^–11 cm²/s and changes insignificantly at these intercalation degrees.     

Sulfurization of polymers. 4. Poly(4,5,6,7-tetrathiono-4,5,6,7-tetrahydrobenzothiophene-2,3-diyl) and related structures based on polystyrene and elemental sulfur

Polystyrene was exhaustively sulfurized with elemental sulfur at 190--370 °C to liberate hydrogen sulfide and to form black lustrous powders (the sulfur content was up to 67%) possessing conductivity (10^–7--10^–6 S cm^–1 upon doping with I₂), paramagnetic properties ((3.4--13)·10¹⁹ sp g^–1, g = 2.0040--2.0046, H = 0.36--0.47 mT), and redox properties. The use of these polymers as active cathode materials in lithium batteries allows their repeated cycling at a specific discharge capacity of up to 330 mA h g^–1. The data of elemental analysis and differential scanning calorimetry, the IR and ESR spectra, the conductivities, and the character of electrochemical activity of the polymers synthesized are consistent with poly(4,5,6,7-tetrathiono-4,5,6,7-tetrahydrobenzothiophene-2,3-diyl) and related structures.     

Electrochemical performance of sulfur composite cathode materials for rechargeable lithium batteries

The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery.In this paper,sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon,which is characterized as high specific surface area and microporous structure.The composite,contained 70%sulfur,as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature....     

Electric Properties of Solid Solutions in the Systems Li6MoN4−Li7NbN4 and Li6WN4−Li7TaN4

The phase balance and electric properties of products in the systems Li₆MoN₄–Li₇NbN₄ and Li₆WN₄–Li₇TaN₄ are studied. It is shown that continuous series of solid solutions whose lithium-cation conductance decreases during mutual doping exist in either system. The activation energies for the long- and short-range motion of lithium charge carriers, determined from the electroconductance and ⁷Li NMR data, equal 55 and 46 or 25 and 14 kJ mol^–1 for the initial compounds of the first and second systems, respectively. The difference that large is attributed to a large contribution of the coulombic correlation for the hops of lithium charge carriers in both systems. Basic parameters of the correlation (time, distance, relaxation time) are calculated from experimental data. The strong correlation in the systems is presumed to stem from a weak screening of the coulombic field in the nitrides, rather than from a high concentration of charge carriers.     

Electrochemical Intercalation of Lithium into Graphite in Acetonitrile Solutions: The Effect of the Anion Nature

Effect of the anion nature on the cathodic intercalation of lithium into graphite is studied. The duration of a discharge process and the capacity of Li _x C₆ electrodes increase in the row Cl^– HSO₄ ^– < ClO₄ ^– < SCN^–. The highest negative potential of an Li _x C₆ electrode is reached when lithiating in an LiSCN non-aqueous solution. X-ray diffraction and microstructure analyses confirm the presence in the electrode's upper layers of predominantly layered compounds Li _x C₆A _y , where A is anion. In deep layers, the principal intercalation product is Li _x C₆.     

Raman spectra in the libration region of concentrated aqueous solutions of lithium-6 and lithium-7 halides. Evidence for tetrahedral Li(OH2) 4 +

The Raman spectra of saturated solutions of⁶LiCl and⁷LiCl have been decomposed into Gaussian components, one of which is a polarized band that occurs at 360 cm^–1 when the ion is⁶Li⁺ and shifts to 335 cm^–1 when the ion is⁷Li⁺. Equivalent bands occur in the spectra of saturated solutions of⁶LiBr and⁷LiBr at 343 and 320 cm^–1, respectively. These bands are assigned to solvent-separated ion aggregates. The Raman spectra of 8.0 and 3.5 m solutions of the isotopic lithium chlorides have been decomposed into five Gaussian components, three of which are assigned to water librations. In addition, there is a polarized band at 440 cm^–1 independent of the lithium isotope used, and a depolarized band which occurs at 385 cm^–1 in the⁶LiCl solutions and 360 cm^–1 in the⁷LiCl solutions. We interpret these two additional bands as theA ₁ andF ₂ stretching modes of Li⁺ tetrahedrally solvated by water molecules.     

Lithium electrochemistry of NiSe2: A new kind of storage energy material

NiSe₂ thin film has been successfully fabricated by reactive pulsed laser deposition and was investigated for its electrochemistry with lithium for the first time. The reversible discharge capacities of NiSe₂/Li cells cycled between 1.0 V and 3.0 V were found in the range of 314.9–467.5 mA h g⁻¹ during the first 200 cycles. By using ex situ X-ray diffraction, transmission electron microscopy, and selected-area electron diffraction measurements, the intermediates of β-NiSe, and Ni₃Se₂ were identified during the reversible conversions of NiSe₂ into metal nickel and Li₂Se. Both cation (nickel) and anion (selenium) in NiSe₂ provide the redox active centers in its electrochemical reaction with lithium, indicating one of the features of its lithium electrochemistry. The high reversible capacity and good cycle ability of NiSe₂ electrode made it become a promising cathode material for future rechargeable lithium batteries.     

The effect of polyether ligands on the solution structure of [Li]-α-(phenylthio)benzyllithium in tetrahydrofuran: A H,Li-HOESY NMR study

[⁶Li]-α-(phenylthio)benzyllithium 1-⁶Li was studied in THF/[D₈]THF solution (1:1) in the presence of several acyclic and cyclic polyether ligands by ¹H,⁶Li-HOESY, ¹H and ¹³C NMR spectroscopy. The question whether these ligands are bonded to lithium or not is important for physical–organic investigations as well as for studies of the ground state of (stereoselective) reactions of organolithium compounds in the presence of such ligands. Dimethoxyethane is not bonded to lithium under these conditions. The acyclic ethers diglyme and triglyme coordinate only weakly to the organolithium compound and form contact ion pairs (CIPs) at 25°C. At −80°C, CIPs are in equilibrium with separated ion pairs (SIPs). Very stable complexes of 1-⁶Li are obtained with crown ether ligands. Addition of 12-crown-4 and 15-crown-5, respectively, results in the exclusive formation of SIPs at 25°C and −80°C. With 18-crown-6, a CIP–SIP equilibrium is observed at 25°C which is shifted entirely to the SIP side at −80°C. Graphical analyses of the ¹H and ¹³C NMR spectra of the polyether complexes of 1-⁶Li revealed correlations between the chemical shifts of the para phenyl carbon C-5, the para phenyl proton H-5, the benzylic carbon C-1, and the proton–carbon coupling constant J(C-1,H-1) of 1-Li, which are useful probes for the charge distribution within the carbanionic moiety of 1-⁶Li in the respective complexes, and thus for the ion pair character as a function of the polyether complexation of lithium.     

Electropolymerization of ionic liquid substituted polyphenylene as supercapacitors materials

A new type of polyphenylene, ionic liquid (IL) 1,3-methylimidazolium hexafluorophosphate substituted, has been prepared by electrodeposition on Au electrode surface via pulse galvanostatic method in 1-butyl-3-methylimidazolium hexafluorophosphate solution. The obtained polymer film had a spherulitic morphology with smallest grains of around 500 nm. Infrared spectrometry revealed that polyphenylene was deposited to a certain extent. The capacitive behavior of the IL substituted polyphenylene was investigated by cyclic voltammetry (CV) and galvanostatic charge–discharge method in 0.2 mol L⁻¹ H₂SO₄ aqueous solutions or pure IL [bmim]PF₆. The specific capacitance of the polymer at the charge–discharge current density of 1 mA cm⁻² equaled 206 F g⁻¹ in acidic aqueous solution or 164 F g⁻¹ in [bmim]PF₆. Additionally, excellent charge–discharge cycle stability (over 85% value of specific capacitance remained after 600 charge–discharge cycles) and power characteristics of the polymer electrode were observed in both electrolytes.     

Preparation of spherical spinel LiMn2O4 cathode material for lithium ion batteries

A novel process is proposed for synthesis of spinel LiMn₂O₄ with spherical particles from the inexpensive materials MnSO₄, NH₄HCO₃, and NH₃H₂O. The successful preparation started with carefully controlled crystallization of MnCO₃, leading to particles of spherical shape and high tap density. Thermal decomposition of MnCO₃ was investigated by both DTA and TG analysis and XRD analysis of products. A precursor of product, spherical Mn₂O₃, was then obtained by heating MnCO₃. A mixture of Mn₂O₃ and Li₂CO₃ was then sintered to produce LiMn₂O₄ with retention of spherical particle shape. It was found that if lithium was in stoichiometric excess of 5% in the calcination of spinel LiMn₂O₄, the product had the largest initial specific capacity. In this way spherical particles of spinel LiMn₂O₄ were of excellent fluidity and dispersivity, and had a tap density as high as 1.9 g cm^–3 and an initial discharge capacity reaching 125 mAh g^–1. When surface-doped with cobalt in a 0.01 Co/Mn mole ratio, although the initial discharge capacity decreased to 118 mAh g^–1, the 100th cycle capacity retention reached 92.4% at 25°C. Even at 55°C the initial discharge capacity reached 113 mAh g^–1 and the 50th cycle capacity retention was in excess of 83.8%.     

Geminal systems. 15. Chemical properties of N-chloro-N-alkoxy-N-tert-alkylamines

Conclusions N-chloro-N-alkoxy-N-tert-alkylamines react exclusively with CN^– and SCN^– and partially with Et^– and AcO^– to give nucleophilic substitution products at the nitrogen atom. These compounds react with AcO^– and water to give nitroso compounds, with EtS^– and Ph₃ P to give azoxy compounds, and with AgF and AgNO₃ to give products of more complex transformations.For communication 14, see ref. [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2320–2326, October, 1981.     

Kinetic CH-acidity of benzenetricarbonylchromium and its derivatives

Kinetic acidities of aryl and benzyl CH-bonds for complexes of benzene and its methoxy and alkyl derivatives with tricarbonylchromium are determined in a solution of lithium tert-butoxide in N,N-dimethylacetamide. Complexation of alkyl-aromatic compounds to the Cr(CO)3 group increases the lability of the aryl CH-bond by 107–109 times and that of the benzyl bond by 5·10⁴–5·10⁵ times. The Cr(CO)₃ group in arene complexes neutralizes the effect of other substituents regardless of their nature and position in the molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2458–2461, November, 1989.     

Kinetics and mechanism in the decomposition of NH3 in a radio-frequency pulse discharge

Studies of time-resolved absorption spectra of transient species in the decomposition of NH₃ by an r.f. pulse discharge together with product analysis showed that the major radical formed was NH at concentrations of the order of 10^–6 mol dm^–3 (10⁵ molec. cm^–3). Possible mechanisms for the formation of the radical during the discharge and its decay following pulse cut-off were tested by computer simulation of the kinetic data. Following zero-order formation with rate coefficient 0.19±0.03 mol dm^–3 s^–1, the decay was second order in NH with rate coefficient 2.1±0.5×10⁹ mol^–1 dm³ s^–1 both for pure NH₃ and where NH₃/rare gas mixtures were investigated. The kinetic data are consistent with NH removal in a nonassociative radical-radical reaction proceeding via a short-lived collision complex, probably 2NH N₂H₂ N₂ + H₂.     

Decreasing Irreversible Capacity of Graphite Electrodes in Lithium-Ion Batteries by Direct Contact of Graphite with Metallic Lithium

The feasibility of reducing the irreversible capacity of negative graphite electrodes in lithium-ion batteries by a direct contact of such electrodes with lithium in the electrolyte is studied. It is shown that the dynamics of the formation of the passive film on graphite and the degree of the decrease in the irreversible capacity depend on the ratio between weights of graphite and lithium in contact. This method of reducing the irreversible capacity does not diminish the reversible capacity of graphite during the cycling. The irreversible capacity of the initial graphite cycled in 1 M LiPF₆ in a mixture of propylene carbonate and diethyl carbonate at a current density of 20 mA g^–1 is 550–1150 mA h g^–1. The reversible capacity of electrodes cycled in the same conditions reaches 290 mA h g^–1.     

Photometrisch-potentiometrische Bestimmung der Hydrolysenkonstanten vonN-Bromverbindungen

The equilibrium concentrations of all reaction products emerging from the hydrolysis ofN-bromo compounds in the presence of bromide and thereby also the hydrolysis constants (K ₁) have been calculated from the absorbance at 392.8 nm, thepH-value and the initial concentrations of theN-bromo compound and the bromide. The following compounds have been investigated:N-bromo-succinimide:K ₁=2.2·10^–6, 1,3-dibromo-5,5-dimethylhydantoin:K ₁=1.7·10^–5,N-bromoacetamide:K ₁=1.8·10^–6,N-bromo-monochloroacetamide: 5.2·10^–6,N-bromo-dichloroacetamide:K ₁=8.9·10^–6 andN-bromo-trichloroacetamide:K ₁=1.8·10^–5. The precision of the method, which is mainly suited for weak hydrolizingN-bromocompounds (K ₁<10^–4) are discussed and the overall error of the calculated values was found to be in the range of ±5–12%. The reactivities in aqueous solution of the most frequently usedN-bromo compounds are compared by means of the calculated HOBr equilibrium concentrations. The differences to be expected on the basis of the latters are at concentrations >10^–5 mol/l rather great, while they can be neglected in very dilute solutions (-10^–6 mol/l).

     

Electrolytic molybdenum oxides in lithium batteries

Nonstoichiometric molybdenum oxides (e-Mo_xO_y) were synthesized by cathodic reduction of aqueous ammonium and sodium molybdate solutions. Surface morphology of electrolytic (e) deposits, the chemical composition, crystal lattice structure, and the characteristics of electrochemical Li⁺ intercalation for such synthesized oxides were determined by the cation composition of molybdate solution and the conditions of deposit annealing. The electrochemical intercalation of Li⁺ ions in these Mo-oxides was investigated in thin-layer ballast-free electrodes, as a pasted mposite cathode in lithium batteries, and as an anode in lithium-ion batteries, with liquid organic and polymer electrolytes. The reversible discharge capacity of e-Mo₄O₁₁ synthesized from ammonium molybdate electrolyte in thin-layer ballast-free electrodes can exceed 225 mAh g^–1 for more than 170 cycles.     

Vibrational spectroscopic and density functional theory studies on ion solvation and ion association of lithium tetrafluoroborate in N,N-dimethylcarbamoyl chloride-based solvents

Solvation and association interactions in solutions of LiBF₄/DMCC (DMCC for N,N-dimethylcarbamoyl chloride) and LiBF₄/DMCC–DME (DME for 1,2-dimethoxyethane) have been studied as a function of concentration of lithium tetrafluoroborate by infrared and Raman spectroscopy. Strong interactions between Li⁺ and solvent molecules or BF₄⁻ anions are observed. The apparent solvation numbers of Li⁺ in LiBF₄/DMCC solutions were deduced. Band-fitting to the B–F stretching band of BF₄⁻ anion permits detailed assess of the ion pairing. Based on the calculations of density function theory, optimal structures of Li⁺(DMCC)_n (n = 1–3) were suggested. It is found that the lithium ion was preferentially solvated by DME in DMCC–DME binary solvents. This finding is supported by quantum chemistry calculations.     

Monte Carlo Simulation of Radiation Trapping in Hg–Ar Fluorescent Discharge Lamps

The line spectra of emitted resonance radiation from mercury and the effective decay rates of the Hg 6³P₁ and 6¹P₁ levels in mercury–argon discharges are simulated by a Monte Carlo method. The hyperfine splitting, the natural isotopic composition, collisional transfer of excitation, foreign gas collisions and quenching are considered to describe in detail the 253.7 nm and 184.9 nm lines. The calculations are performed for Hg vapor densities corresponding to coldest spot temperatures of 5–100°C, and discharge parameters typical for fluorescent lamp operation. The densities of the Hg 6³P₁ and 6¹P₁ levels are consistently estimated by means of a set of balance equations for the Hg 6³P₀, 6³P₁, 6³P₂, and 6¹P₁ excited states. The resulting uv radiation output of the discharge is then estimated for a tube radius of 18 mm, argon pressure of 400 Pa, discharge current 0.4 A, and wall temperatures of 20–80°C. The results obtained show a good agreement as compared with published experimental data.     

Gas-phase reactions in plasmas of SF6 with O2 in He

Processes which occur in microwave discharges of dilute mixtures of SF₆ and O₂ in He have been examined using a flow reactor sampled by a mass spectrometer. Two classes of experiments were performed. In the first set of experiments, mixtures containing 6×10¹¹ cm^–3 SF₆, 6×10¹⁶ cm^–3 He, and O₂ in the range (0–3.6)×10¹³ cm^–3 were passed through a 20-W 2450-MHz microwave discharge. The gas mixtures arriving at a sample point downstream from the discharge were examined for SF₆, SF₄, SOF₂, SOF₄, SO₂F₂, SO₂, F, and O. In the second class of experiments, rate coefficients were measured for the reactions of SF₄ with O and O₂ and for the reaction of SF with O. The rate coefficient for the reaction of SF with O was found to be (4.2±1.5)×10^–11 cm^–3 s^–1. SF₄ was found to react so slowly with both oxygen atoms and oxygen molecules that only upper limits could be placed on the rate coefficients for these reactions. These values were 2×10^–14 cm³ s^–1 and 5×10^–15 cm³ s^–1 for reactions with O and O₂ respectively. The observed distribution of products from the discharged mixtures is discussed in terms of the measured rate coefficients.