A study of cokes used as anodic materials in lithium ion rechargeable batteries

A variety of cokes pretreated at different temperatures are used as anodic materials and their electrochemical characteristics are examined by cyclic voltammetry. It is found that for some cokes such as petroleum coke (preheated at 1300 degrees C), pitch coke (1300 degrees C), needle coke (1900 degrees C), metallurgical coke (1900 degrees C), high capacity and cyclic efficiency are achieved. Needle coke (1900 degrees C) and metallurgical coke (1900 degrees C) in particular give a capacity of over 200 mAh/g and a cyclic efficiency of nearly 100%, whereas poor performance is exhibited by those pretreated at higher or lower temperatures, e.g., petroleum cokes (500 degrees C, 2800 degrees C), pitch coke (500 degrees C) and needle coke (2800 degrees C). The cyclic voltammograms show two electrochemical processes, one at about 0.1 V vs. Li+/Li which is electrochemically reversible, and may be attributed to the intercalation/deintercalation of lithium ions while the other, at about 0.6 V vs. Li+/Li, is electrochemically irreversible and may be assigned to the decomposition of the electrolyte solvent, which leads to formation of the passive film on the anode surface. The experimental results strongly suggest that the pretreatment temperature of cokes and of the solvent are determining factors for the growth, structure and properties of the passive film.

Lithium ion conducting polymer electrolytes based on alternating maleic anhydride copolymer with oligo-oxyethylene side chains

A comb polymer with oligo-oxyethylene side chains of the type -(CH2CB2O)(12)CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer and poly (ethylene glycol) methyl ether. The polymer can dissolve LiClO4 salt to form homogeneous amorphous polymer electrolyte. The ac ion conduction was measured using the complex impedance method, and conductivities were investigated as functions of temperatures and salt concentration. The complexes were first found to have two classes of glass transition which increase with increasing salt content, The optimum conductivity attained at 25 degrees C is in the order of 5.50 x 10(-6)Scm(-1). IR spectroscopy was used to study the cation-polymer interaction.

Carbon materials for lithium ion batteries

The preliminary work indicated that passive film is the most important factor influencing cell performance of carbon anode, and the carbon and solvent used govern cell performance by forming the passive film of different properties. A in situ XRD result is also presented.

TRIS(TERT-BUTYLCYCLOPENTADIENYL)NEODYMIUM-MU-CHLORO-TRIS(TETRAHYDROFURAN)LITHIUM, [ND(ETA(5)-(T)BUCP)3(MU-CL)LI(THF)3]

The title complex, tris[2(eta5)-tert-butylcyclopentadi-enyl]-mu-chloro-1:2kappa2Cl-tris(tetrahydrofuran-1kappaO)lithiumneodymium, [Nd(C9H13)3(mu-Cl)Li(C4H8O)3], consists of the neutral moiety ((t)BuCp)3Nd linked to the cation [Li(thf)3]+ by a mu-Cl bridge

Role of Lithium in Multicomponent Oxide Catalysts for Oxidative Coupling of Methane

The effect of Li content in a series of multicomponent oxides LixLa0.5Ti0.5 For methane oxidative coupling has been studied. The catalytic activities of LiLa0.5Ti0.5 catalyst before and after washing with boiling water have been compared. The surface and

IMPEDANCE STUDY OF THE INTERFACES BETWEEN LITHIUM, POLYANILINE, LITHIUM-DOPED MNO2 AND MODIFIED POLY(ETHYLENE OXIDE) ELECTROLYTE

Impedance study was carried out for the interfaces between lithium, polyaniline (PAn), lithium-doped MnO2 and modified poly(ethylene oxide) (PEO) electrolyte under various' conditions. The interfacial charge-transfer resistances R(ct) on PEO/PAn, R(ct) on PEO/LiMn2O4 increase with depth-of-discharge and decrease after the charge of the cell containing modified PEO as electrolyte. The charge-transfer resistance R(ct) on PEO/PAn is higher than R(ct) on PEO/LiMn2O4 under the same condition, since inserted species and mechanism are different for both cases. In the case of PAn, an additional charge-transfer resistance might be related to the electronic conductivity change in discharge/charge potential range, as it was evident from a voltammetry curve. With increasing cycle numbers, the charge-transfer resistance increases gradually. The impedance results also have shown that at low frequency the diffusion control is dominant in the process of the charge and discharge of Li/PEO/PAn or Li/PEO/LiMn2O4 cell. The diffusion coefficients have been calculated from impedance data.

STUDIES OF SPINEL LICRXMN2-XO4 FOR SECONDARY LITHIUM BATTERY

X-ray and electrochemical studies of spinel-related manganese chromium oxides, LiCrxMn2-xO4 (0 less-than-or-equal-to x less-than-or-equal-to 1) were carried out in a lithium nonaqueous cell. X-ray diffraction spectra indicated that the substitution of manganese in LiMn2O4 by trivalent transition metals (Cr3+) cause the linear decrease of lattice parameter with the x in the LiCrMn2-xO4. Some discharge-capacity loss was obtained due to the lattice contraction of LiCrMn2-xO4, but it has a better rechargeability than LiMn2O4. Cyclic voltammetry and electrochemical impedance experiments have shown that the excellent rechargeability of LiCrxMn2-xO4 may be attributed to the good reversibility of the change in its crystal structure for the insertion and extraction of lithium ions.

DEVELOPMENT OF CYLINDRICAL SECONDARY LITHIUM POLYANILINE BATTERIES

The cylindrical 'D'-size batteries were fabricated by polyaniline paste cathode and lithium foil anode sandwiched with microporous polypropylene separator. The electrolyte used was LiClO4 dissolved in a mixed solvent of propylene carbonate and dimethoxyethane. The results of charge/discharge curves, charge/discharge cycles, the short-circuit current, the open-circuit voltage storage and the change of discharge capacity with temperature, discharge current are reported.

HIGH-TEMPERATURE SUPERCONDUCTOR, YBA2CU3O7-X AS ALL-SOLID-STATE LITHIUM CELL

The utility of the high-temperature superconductor, YBa2Cu3O7-x as the cathode material for an all-solid-state lithium cell has been examined. The capacity of YBa2Cu3O7-x is 223 mA h g-1 and the discharge efficiency is > 92%. Measurements of a.c. impedance show that the charge-transfer resistance at the interface of the electrolyte/cathode is very low and increases with the depth-of-discharge of the battery. Studies using X-ray photoelectron spectroscopy (XPS) reveal that the cathode becomes doped with Li+ ions as the cell discharges.

AN ALL-SOLID-STATE LITHIUM POLYANILINE RECHARGEABLE CELL

The performance of an all-solid-state cell having a lithium negative electrode, a modified polyethylene oxide (PEO)-epoxy resin (ER) electrolyte, and a polyaniline (PAn) positive electrode has been studied using cyclic voltammetry, charge/discharge cycling, and polarization curves at various temperatures. The redox reaction of the PAn electrode at the PAn/modifed PEO-ER interface exhibits good reversibility. At 50-80-degrees-C, the Li/PEO-ER-LiClO4/PAn cell shows more than 40 charge/discharge cycles, 90% charge/discharge efficiency, and 54 W h kg-1 discharge energy density (on PAn weight basis) at 50-mu-A between 2 and 4 V. The polarization performance of the battery improves steadily with increase in temperature.

A WOUND-TYPE LITHIUM POLYANILINE SECONDARY CELL

A wound-type cell with a polyaniline (PAn) positive electrode, a LiClO4-propylene carbonate (PC) electrolyte, and a lithium foil negative electrode has been constructed. The two electrodes are separated by a polypropylene separator. The PAn is deposited on carbon felt from a HClO4 solution containing aniline by galvanostatic or potentiostatic electrolysis. Using cyclic voltammetry charge/discharge cycles and charge/retention tests, the following results have been obtained: (i) reversibility of the charge/discharge reaction of the PAn electrode is very good; (ii) more than 50 charge/discharge cycles at 80% charge/discharge efficiency and 260 W h kg-1 discharge energy density can be achieved at 50 mA between 2 and 4 V; (iii) the open-circuit voltage and the capacity retention of the battery after storage at open-circuit for 60 days are 3.4 V and 33%, respectively.

SYNTHESIS OF ALKALI-METAL HYDRIDES USING LANTHANIDE TRICHLORIDE-NAPHTHALENE AS CATALYST UNDER MILD CONDITIONS

The hydrogenation of alkali metals using lanthanide trichloride and naphthalene as catalyst has been studied. LnCl3(Ln = La, Nd, Sm, Dy, Yb) and naphthalene can catalyze the hydrogenation of sodium under atmospheric pressure and 40-degrees-C to form sodium hydride. The activities of lanthanide trichlorides are in the following order: LaCl3 > NdCl3 > SmCl3 > DyCl3 > YbCl3. Although lithium proceeds in the same catalytic reaction, the kinetic curve of the lithium hydrogenation is different from that of sodium. Lanthanide trichlorides display no catalytic effect on the hydrogenation of potassium in presence of naphthalene. The mechanism of this reaction has been studied and it is suggested that the anion-radical of alkali metal naphthalene complexes may be the intermediate for the hydrogenation of alkali metals and the function of LnCl3 is to catalyze the hydrogenation of the intermediate. The products are porous solids with high specific surface area (83 m2/g for NaH) and pyrophoric in air. They are far more active than the commercial alkali metal hydrides. The combination of these hydrides with some transition metal complexes exhibits high catalytic activity for the hydrogenation of olefins.

STUDY ON DEPOSITION POTENTIALS OF LITHIUM AND SODIUM-IONS AND DEPOLARIZATION IN BINARY CHLORIDE

Deposition potentials of Lithium and Sodium ions have been measured in binary chloride systems (LiCl-KCl, NaCl-KCl) by I-V curve method, to provide a theoretical base for preparing high purity Al-Li alloy by electrolysis in molten salt. The changes of free energy and enthalpy were calculated in terms of depolarization values on Al cathode. Thermodynamic meaning of depolarization was discussed in details and the empirical relation between binary alloy type and depolarization type was proposed. It is shown for the first time that the presence of a third element in Al-Li alloy can strengthen depolarization of Li ion at Al alloy cathode and give foundation for preparing high purity Al-Li-M ternary alloy. The effect of LiCl concentration on deposition potentials of Li ion at Al cathode in KCl-LiCl melt was studied and average active coefficient of LiCl was obtained.

STUDY OF BIMETALLIC COMPLEXES OF RARE-EARTH LITHIUM - SYNTHESIS AND CRYSTAL-STRUCTURE OF THE (LACL)DME(MU-2-CL)5(MU-3-CL) (LA.DME)LI(THF)2

The reaction between LaCl_3 and LiCl in THF at room temperature, with hexane as precipitant and glycol dimethyl ether as complexing agent, has been studied. A complex with the composition of (LaCl)DME(μ_2-Cl)_5(μ_3-Cl)(La·DME)Li(THF)_2 has been synthesized, its structure was studied by single crystal X-ray diffraction technique. The diffraction intensities were collected at about —100℃. The complex belongs to the triclinic space group P1 with α=11.123(3), 6=16.564(5), c=8.653(3)A, α=95.16(3), β=...

Determination of trace arsenic and selenium in jellyfish by microwave digestion-hydride generation-atomic fluorescence spectrometry

A method of hydride generation-atomic fluorescence spectrometry was proposed in the present paper for the determination of trace arsenic and selenium in jellyfish. The samples were treated by the combination of microwave digestion and lyophilization. The optimal conditions for treating and analyzing samples were established. The problem of the effect of the superfluous acid in the digesting solution on the results was solved, and the influence of coexisting foreign ions on the determination of arsenic and selenium was investigated. The accuracy of the method was confirmed by the method of standard additions. This method proved to be simple, rapid and repeatable, and is suitable for the analysis of biologic samples containing water.