Improved electrochemical properties of chromium substituted in LiCr1 ? x Ni x O2 cathode materials for rechargeable lithium-ion batteries

Pristine- and chromium-substituted LiNiO₂ nanoparticles were synthesized by sol-gel method using nitrate precursor at 800?°C for 12?h. Physical properties of the synthesized product were analyzed using Fourier transform infrared, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive analysis X-ray. XRD studies revealed a well-defined layer structure and a linear variation of lattice parameters with the addition of chromium and no impurities. Surface morphology and particle size of synthesized materials were changed with chromium addition using SEM and TEM analyses. Assembled lithium-ion cells were evaluated for charge/discharge studies at different rates, cyclic voltammetry, and electrochemical impedance spectra. The initial discharge capacity of LiNiO₂ cathode material was found to be 168?mA hg^?1; however, discharge capacity increased in chromium substitution. Electrochemical impedance spectroscopy revealed that LiCr_0.10Ni_0.90O₂ could enhance charge transfer resistance upon cycling. The substitution of Ni with chromium, LiCr_0.10Ni_0.90O₂, had better cycle life, low irreversible capacity, and excellent electrochemical performance.     

Mixed crystal formation and structural studies in the mullite-type system Bi2Fe4O9–Bi2Mn4O10

The limits of metal cation substitution and distribution in the sequence Bi₂Fe₄O₉–Bi₂Mn₄O₁₀ have been investigated by solid state synthesis, X-ray powder diffraction, and Mössbauer spectroscopy. Rietveld refinements conducted for the entire range along the join indicate the structures are orthorhombic with space group Pbam, with partial transition-metal site disorder confirmed and detailed by Mössbauer spectroscopy. Single-phase regions are found near each end-member and a two-phase region is observed at intermediate compositions, extending from about x=1 to 3, according to the general formula of the mixed crystals Bi₂Fe_4?xMn_xO_10?δ. An incorporation of Mn at octahedral sites replacing Fe is taken into account for the Bi₂Fe₄O₉-related side of the system. Charge compensation is believed to be effected by addition of O, which gives rise to the formation of FeO₅ pyramids. At the Bi₂Mn₄O₁₀-related side of the system, substitution of pyramidal Mn³⁺ by Fe³⁺ is envisaged.     

Electric conductivity of solid solutions in Cs2 ? 2x Fe2 ? x A x O4 systems (A = P, V)

Solid solutions based on CsFeO₂ in Cs_{2 ? 2x} Fe_{2 ? x} A _x O₄ systems (A = P, V) were synthesized. Their crystal structure and the temperature and concentration dependences of the total conductivity and its electronic component were studied. The ranges of temperature and composition in which cesium-cation conductivity was dominant were determined. The obtained data were compared with the results of studies of other cesium-conducting solid electrolytes.     

Electrochemical studies of LiMnPO4 as aqueous rechargeable lithium–ion battery electrode

A study of the electrochemical behavior of LiMnPO₄ prepared by RAPET method in different aqueous electrolytes using cyclic voltammetry (CV), galvanostatic charge–discharge experiments, and electrochemical impedance spectroscopy is reported. CV peak current is proportional to the square root of scan rate under 0.2 mV s⁻¹. The system satisfied the required conditions for a reversible system with a resistive behavior. LiMnPO₄ was found to undergo proton insertion at lower concentrations of electrolyte. At higher concentrations or saturated solutions of electrolytes, lithium insertion/de-insertion becomes the main reaction though the effect of proton insertion/de-insertion reaction cannot be ignored. Electrochemical insertion/de-insertion of lithium in LiMnPO₄ was studied using EIS technique. The kinetic parameter, charge transfer resistance (R _ct), obtained by simulating the experimental impedance data with an equivalent circuit showed a minimum at the potential close to the CV peak potential. The cell LiTi₂(PO₄)₃/5 M LiNO₃/LiMnPO₄ delivers a discharge capacity of 84 mAh g⁻¹ in the first cycle at an applied current of 0.2 mA cm⁻² and it retains its initial capacity over 50 cycles with good rate capability.     

Electrochemical reactivity of Li–Mn–O and Li–Fe–Mn–O spinels

Electrochemical reductive dissolution of Li–Mn–O and Li–Fe–Mn–O spinels and Li⁺ extraction/insertion in these oxides were performed using voltammetry of microparticles. Both electrochemical reactions are sensitive to the Fe/(Fe+Mn) ratio, specific surface area, Li content in tetrahedral positions, and Mn valence, and can be used for electrochemical analysis of the homogeneity of the elemental and phase composition of synthetic samples. The peak potential (E _P) of the reductive dissolution of the Li–Mn–O spinel is directly proportional to the logarithm of the specific surface area. E _P of Li–Fe–Mn–O spinels is mainly controlled by the Fe/(Fe+Mn) ratio. Li⁺ insertion/extraction can be performed with Mn-rich Li–Fe–Mn–O spinels in aqueous solution under an ambient atmosphere and it is sensitive to the regularity of the spinel structure, in particularly to the amount of Li in tetrahedral positions and the Mn valence. Electronic Publication     

Characterization of superparamagnetic Mg x Zn1−x Fe2O4 powders

Structural and magnetic properties of Mg _x Zn_1−x Fe₂O₄ powders have been studied with respect to the application for thermal cancer therapy (magnetic hyperthermia). Mg _x Zn_1−x Fe₂O₄ (x=0.1–0.5) powders with particle sizes between 5 and 8 nm were produced by citrate method. The X-ray diffraction patterns of the samples correspond to a spinel phase. The lattice constant and the volume of the elementary cell increase when x changes from 0.1 to 0.5. The FTIR-spectra ascertain the spinel phase formation. The Mossbauer studies reveal the presence of extremely small particles, which undergo superparamagnetic relaxation at room temperature. The core-shell model has been applied to explain quadruple doublets. The quadruple splitting at “shells” is bigger than those at “cores” whereas the isomer shifts remain close. Magnetic studies confirm the presence of extremely small particles that behave as superparamagnetic ones.      

Electrochemical reduction of NO and O2 on La2−x Sr x CuO4-based electrodes

A series of La_2 − x Sr _x CuO₄ (x = 0.0, 0.05, 0.15, 0.25 and 0.35) compounds was investigated for the use of direct electrochemical reduction of NO in an all-solid-state electrochemical cell. The materials were investigated using cyclic voltammetry in 1% NO in Ar and 10% O₂ in Ar. The most selective electrode material was La₂CuO₄, which had an activity of NO reduction that was 6.8 times higher than that of O₂ at 400 °C. With increasing temperature, activity increased while selectivity decreased. Additionally, conductivity measurements were carried out, and the materials show metallic conductivity behavior which follows an adiabatic small polaron hopping mechanism.     

Synthesis and Electrochemical Performance of Spinel LiMn2O4—x（SO4）x Cathode Materials

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｒｅｃｅｎｔｙｅａｒｓ ,ｗｉｔｈｔｈｅｄｅｖｅｌｏｐｍｅｎｔｏｆａｌｌｓｏｒｔｓｏｆｃｅｌｌｕｌａｒｐｈｏｎｅｓ ,ｃａｍｃｏｒｄｅｒｓ ,ｌａｐｔｏｐｃｏｍｐｕｔｅｒｓ ,ｔｈｅｌｉｔｈｉｕｍ ｉｏｎｓｅｃｏｎｄａｒｙｂａｔｔｅｒｉｅｓｂａｓｅｄｏｎｔｈｅｕｓｅｏｆｌｉｔｈｉ ｕｍ ｍａｎｇａｎｅｓｅ ｏｘｉｄｅＬｉＭｎ2 Ｏ4 1,2 ｈａｖｅａｔｔｒａｃｔｅｄｍｕｃｈａｔ ｔｅｎｔｉｏｎ .ＢｕｔｔｈｅＬｉＭｎ2 Ｏ4 ｃａｔｈｏｄｅｍａｔｅｒｉａｌｈａｓａｄｉｓａｄ ｖａｎｔａｇｅｏｆ…     

电解液对LiCr0.1Mn1.9O4电化学性能的影响

容量;循环特性;自放电;电解液对LiCr0.1Mn1.9O4电化学性能的影响     

Surface tension studies on the complexation of dodecylpyridinium chloride byβ-cyclodextrin in aqueous electrolyte solutions

Surface tension measurements have been performed at 25° C for aqueous mixtures of dodecylpyridinium chloride and -cyclodextrin in 0.1 M NaCl. Data analyses assuming 1:1 stoichiometry were applied to estimate the complexation constant of the host-guest complex formation. The technique yields consistent results for solutions with a swamping, constant concentration of a simple inorganic electrolyte.     

Synthesis, characterization, infrared studies, and thermal analysis of Mn0.6Zn0.4Fe2(C4H2O4)3·6N2H4 and its decomposition product Mn0.6Zn0.4Fe2O4

Manganese zinc ferrous fumarato–hydrazinate precursor, Mn_0.6Zn_0.4Fe₂(C₄H₂O₄)₃·6N₂H₄ was synthesized for the first time and characterized by chemical analysis, infrared spectral studies, and thermal analysis. Infrared studies show band at 977 cm^?1 indicating bidentate bridging nature of the hydrazine in the complex. Thermogravimetric (TG) studies show two steps dehydrazination followed by two steps total decarboxylation. The precursor on touching with burning splinter undergoes self propagating autocatalytic decomposition yielding ultrafine Mn_0.6Zn_0.4Fe₂O₄. XRD studies confirms single phase formation as well as nanosize nature of “as prepared” Mn_0.6Zn_0.4Fe₂O₄. The saturation magnetization of the “as prepared” Mn_0.6Zn_0.4Fe₂O₄ was found to be 31.46 emu gm^?1, which is lower than the reported, confirms the ultrafine nature of the oxide.     

Sol–gel synthesized high anisotropy magnetic nanoparticles of NiCr x Fe2−x O4

The nanoparticles of NiCr _x Fe_2?x O₄ were synthesized through sol–gel reactions involving nitrates of Ni, Cr and Fe in an aqueous medium containing citric acid. The cubic spinel structure in single phase with nanometric crystallite size of ~5 nm, the spherical morphology and magnetic relaxations were examined through XRD, TEM and Mössbauer techniques. The abnormal occurrence of finite remanance (M _r ) and coercivity (H _c ) resulted in the room temperature dc magnetization measurements for the small particles authenticate the ferrimagnetic regime, as proposed by the room temperature Mössbauer results of the samples, with a proximate superparamagnetic regime still at lower particle volumes. This could be attributed to the antiferromagnetic spin interactions of chromium ions at octahedral sites and subsequently the over-occupancy of the rest of the cations at tetrahedral sites. In justification to this, the magnetocrystalline anisotropy constant, K, is estimated to have value relatively high of the order of 10⁷ erg/cm³ at room temperature for all studied concentrations.     

Pulse radiolysis studies of vitaminK1 in an aqueous–organic mixed solvent

Pulse radiolysis studies of VK₁ were carried out in a nitrogen-saturated aqueous–isopropanol–acetone mixed solvent. We studied the spectroscopic characteristics of semiquinone radicals of VK₁ and determined the kinetic parameters of formation and decay of the species. It was found that the decay process of semiquinone radicals of VK₁ was according to a first-order reaction, this was different from the case in ethanol solution, possible reasons were also analyzed.     

Electrochemical oxidation of solid Li2O2 in non-aqueous electrolyte using peroxide complexing additives for lithium–air batteries

Using the anion receptor tris(penftafluorophenyl) borane as an additive to non-aqueous electrolytes, the solubility of solid Li₂O₂ can be dramatically increased through the Lewis acid–base interaction between boron and peroxide. The complexed boron-peroxide ions can be electrochemically oxidized with much better kinetics than the oxidation of solid Li₂O₂ on a carbon powder microelectrode. This discovery could lead to a new avenue for the development of high capacity, high rate, rechargeable, Li–Air batteries.     

Pulse radiolysis studies of etoposide and 4′-demethylepipodophyllotoxin in aqueous solution

The reactions of etoposide (VP 16, 4′-demethyl-epipodophyllotoxin ethylidene-β-d-glucoside) and 4′-demethylepipodophyllotoxin (DMEP) with the primary radiolytic products of water, such as e⁻_aq, H and OH/O⁻ radicals, and the secondary radical (SO⁻₄) in aqueous solution were studied by use of the techniques of pulse radiolysis, respectively. The absorption spectra of reaction products with e⁻_aq, H and OH/O⁻ and SO⁻₄ radicals were observed, and the rate constants of them were determined by following the build-up kinetics of radicals produced or the decay of hydrated electron observed at 600 nm, respectively.     

Electrochemical study of spinel oxide systems with nominal compositions Ni1− x Cu x Co2O4 and NiCo2− y Cu y O4

Studies on the electrochemical behaviour of Ni_{1− x} Cu _x Co₂O₄ (x ≤ 0.75) and NiCo_{2− y} Cu _y O₄ (y ≤ 0.30) electrodes in 5 mol dm⁻³ KOH aqueous solutions are presented. The oxide layers have been prepared by thermal decomposition of aqueous nitrate solutions on nickel supports at 623 K. Powder samples were also prepared by thermal decomposition under the same conditions. The powder samples and the oxide layers were characterised by X-ray powder diffraction. The influence of the copper content on the voltammetric response of the electrodes and activity towards oxygen evolution reaction is analysed and correlated with the surface composition of the electrodes by means of X-ray photoelectron spectroscopy data. The analysis of the results reveals that the presence of Cu affects the electrode behaviour and its influence depends on which cation has been replaced. Received: 22 February 1999 / Accepted: 26 October 1999     

Hydration and forms of oxygen-hydrogen groups in Oxyfluorides Ba2 ? 0.5x In2O5 ? x F x

A number of fluorine-substituted compounds were synthesized from brownmillerite Ba₂In₂O₅. The homogeneity range of the Ba_{2 ? 0.5x} In₂O_{5 ? x} F _x solid solution (x ?? 0.3) was determined by X-ray diffractometry. The studied phases were found to be able to incorporate water from the gas phase, due to which their orthorhombic structure transforms into tetragonal one. The degree of hydration decreased as the fluorine content in the solid solution increased. As in the case of Ba₂In₂O₅, the energetically nonequivalent hydroxo groups were found to be the main form of oxygen-hydrogen groups.     

Electrophysical properties of solid solutions of Zn2 − x (Zr a Sn b )1 − x Fe2x O4 compositions

The electrophysical properties of the multicomponent Zn₂ZrO₄ ? Zn₂SnO₄ ? ZnFe₂O₄ system are studied. The electrophysical parameters of solid solutions of Zn_{2 ? x} (Zr _a Sn _b )_{1 ? x} Fe_2x O₄ (x = 0–1.0, Δx = 0.1, a + b = 1) are determined. It is found that the formed solid solutions are semiconductors with electrophysical properties that change in a regular fashion with composition and are distinguished by high values of resistivity (107–1012 Ω cm).     

Synthesis and electrochemical properties of nanostructured LiAl x Mn2 − x O4 − y Br y particles

Nanostructured LiAl _x Mn_2 − x O_4 − y Br _y particles were synthesized successfully by annealing the mixed precursors, which were prepared by room-temperature solid-state coordination method using lithium acetate, manganese acetate, lithium bromide, aluminum nitrate, citric acid, and polyethylene glycol 400 as starting materials. X-ray diffractometer patterns indicated that the particles of the as-synthesized samples are well-crystallized pure spinel phase. Transmission electron microscopy images showed that the LiAl _x Mn_2 − x O_4 − y Br _y samples consist of small-sized nanoparticles. The results of galvanostatic cycling tests revealed that the initial discharge capacity of LiAl_0.05Mn_1.95O_3.95Br_0.05 is 119 mAh g⁻¹; after the 100th cycle, its discharge capacity still remains at 92 mAh g⁻¹. The introduction of Al and Br in LiMn₂O₄ bring a synergetic effect and is quite effective in increasing the capacity and elevating cycling performance.     

Magnetic properties of Cu0.5Fe0.5 ? x Ga x Cr2S4 solid solutions

Solid solutions between ferrimagnet Cu_0.5Fe_0.5Cr₂S₄ (T _C = 347 K) and antiferromagnet Cu_0.5Ga_0.5Cr₂S₄ (T _N = 31 K) have been synthesized, and their magnetic properties studied. Both compounds belong to the A _0.5 ⁺ A _0.5 ³⁺ Cr₂X₄ group with the 1 : 1 order of A⁺ and A³⁺ ions in the tetrahedral spinel sites. Measurements on a SQUID magnetometer over wide ranges of fields (0.05?C40 kOe) and temperatures (5?C300 K) provided a deeper insight into the nature of magnetism and cation distribution in the studied samples.