Ion transport studies in lithium phospho-molybdate glasses containing Cl- ion

Ion conducting glasses in xLiCl-20Li(2)O-(80-x) 0.80P(2)O(5)-0.20MoO(3)] glass system have been prepared over a wide range of composition (X = 5, 10, 15, 20 and 25 mol%). The electrical conductivity and dielectric relaxation of these glasses were analyzed using impedance spectroscopy in the frequency range of 10 Hz-10 MHz and in the temperature range of 313-353 K. D.c. activation energies extracted from Arrhenius plots using regression analysis, decreases with increasing LiCl mol%. A.c. conductivity data has been fitted to both single and double power law equation with both fixed and variable parameters. The increased conductivity in the present glass system has been correlated with the volume increasing effect and the coordination changes that occur due to structural modification resulting in the creation of non-bridging oxygens (NBO's) of the type O-Mo-O- bonds in the glass network. Dielectric relaxation mechanism in these glasses is analyzed using Kohlrausch-Williams-Watts (KWW) stretched exponential function and stretched exponent (beta) is found to be insensitive to temperature.

Ellagic acid - a novel organic electrode material for high capacity lithium ion batteries

Ellagic acid, a naturally occurring polyphenol, extracted from pomegranate husk, is found to be a very good organic electrode material for rechargeable lithium batteries with high reversible capacities of similar to 450 and 200 mA h g(-1) at C/10 and C/2.5 discharge rates, respectively; ex situ NMR studies reveal possible lithiation-delithiation modes at different stages of the charge-discharge process.

Li3MRuO5 (M = Co, Ni), new lithium-rich layered oxides related to LiCoO2: promising electrochemical performance for possible application as cathode materials in lithium ion batteries

We describe the synthesis and crystal structure of Li3MRuO5 (M = Co and Ni), new rock salt related oxides. Both the oxides crystallize in the layered LiCoO2 (alpha-NaFeO2) structure, as revealed by powder XRD data. Magnetic susceptibility data suggest that the oxidation states of transition metals are Li3Co3+(ls)Ru4+(ls) O-5 (ls = low spin) for the M = Co compound and Li3Ni2+Ru5+O5 for the M = Ni compound. Electrochemical investigations of lithium deintercalation-intercalation behaviour reveal that both Co and Ni phases exhibit attractive specific capacities of ca. 200 mA h g(-1) at an average voltage of 4 V that has been interpreted as due to the oxidation of Co3+ and Ru4+ in Li3CoRuO5 and Ni2+ to Ni4+ in the case of Li3NiRuO5. Thus, a different role of Ru ions is played in the isostructural oxides. Finally, in both cases evidence of irreversible behaviour above 4.2 V is observed and interpreted as formation of high valent ions or alternatively oxidation of oxide ions.

Employing synergistic interactions between few-layer WS2 and reduced graphene oxide to improve lithium storage, cyclability and rate capability of Li-ion batteries

The aim of the contribution is to introduce a high performance anode alternative to graphite for lithium-ion batteries (LiBs). A simple process was employed to synthesize uniform graphene-like few-layer tungsten sulfide (WS2) supported on reduced graphene oxide (RGO) through a hydrothermal synthesis route. The WS2-RGO (80:20 and 70:30) composites exhibited good enhanced electrochemical performance and excellent rate capability performance when used as anode materials for lithium-ion batteries. The specific capacity of the WS2-RGO composite delivered a capacity of 400-450 mAh g(-1) after 50 cycles when cycled at a current density of 100 mA g(-1). At 4000 mA g(-1), the composites showed a stable capacity of approximately 180-240 mAh g(-1), respectively. The noteworthy electrochemical performance of the composite is not additive, rather it is synergistic in the sense that the electrochemical performance is much superior compared to both WS2 and RGO. As the observed lithiation/delithiation for WS2-RGO is at a voltage 1.0 V (approximate to 0.1 V for graphite, Li* /Li), the lithium-ion battery with WS2-RGO is expected to possess high interface stability, safety and management of electrical energy is expected to be more efficient and economic. (C) 2013 Elsevier Ltd. All rights reserved.

Excellent Performance of Few-Layer Borocarbonitrides as Anode Materials in Lithium-Ion Batteries

Borocarbonitrides (BxCyNz) with a graphene-like structure exhibit a remarkable high lithium cyclability and current rate capability. The electrochemical performance of the BxCyNz materials, synthesized by using a simple solid-state synthesis route based on urea, was strongly dependent on the composition and surface area. Among the three compositions studied, the carbon-rich compound B0.15C0.73N0.12 with the highest surface area showed an exceptional stability (over 100cycles) and rate capability over widely varying current density values (0.05-1Ag(-1)). B0.15C0.73N0.12 has a very high specific capacity of 710mAhg(-1) at 0.05Ag(-1). With the inclusion of a suitable additive in the electrolyte, the specific capacity improved drastically, recording an impressive value of nearly 900mAhg(-1) at 0.05Ag(-1). It is believed that the solid-electrolyte interphase (SEI) layer at the interface of BxCyNz and electrolyte also plays a crucial role in the performance of the BxCyNz .

C-12 Helices in Long Hybrid (alpha gamma)(n) Peptides Composed Entirely of Unconstrained Residues with Proteinogenic Side Chains

Unconstrained gamma(4) amino acid residues derived by homologation of proteinogenic amino acids facilitate helical folding in hybrid (alpha gamma)(n) sequences. The C-12 helical conformation for the decapeptide, Boc-Leu-gamma(4)(R)Val](5)-OMe, is established in crystals by X-ray diffraction. A regular C-12 helix is demonstrated by NMR studies of the 18 residue peptide, Boc-Leu-gamma(4)(AR)Val](9)-OMe, and a designed 16 residue (alpha gamma)(n) peptide, incorporating variable side chains. Unconstrained (alpha gamma)(n) peptides show an unexpectedly high propensity for helical folding in long polypeptide sequences.

Phase and Dimensionality of Tin Oxide at graphene nanosheet array and its Electrochemical performance as anode for Lithium Ion Battery

We incorporated tin oxide nanostructures into the graphene nanosheet matrix and observed that the phase of tin oxide varies with the morphology. The highest discharge capacity and coulumbic efficiency were obtained for SnO phase of nanoplates morphology. Platelet morphology of tin oxide shows more reversible capacity than the nanoparticle (SnO2 phase) tin oxide. The first discharge capacity obtained for SnO@GNS is 1393 and 950 mAh/g for SnO2@GNS electrode at a current density of 23 mu A/cm(2). A stable capacity of about 1022 and 715 mAh/g was achieved at a current rate of 23 mu A/cm(2) after 40 cycles for SnO@GNS and SnO2@GNS anodes, respectively. (C) 2014 Elsevier Ltd. All rights reserved.

In-situ Stabilization of Tin Nanoparticles in Porous Carbon Matrix derived from Metal Organic Framework: High Capacity and High Rate Capability Anodes for Lithium-ion Batteries

It is a formidable challenge to arrange tin nanoparticles in a porous matrix for the achievement of high specific capacity and current rate capability anode for lithium-ion batteries. This article discusses a simple and novel synthesis of arranging tin nanoparticles with carbon in a porous configuration for application as anode in lithium-ion batteries. Direct carbonization of synthesized three-dimensional Sn-based MOF: K2Sn2(1,4-bdc)(3)](H2O) (1) (bdc = benzenedicarboxylate) resulted in stabilization of tin nanoparticles in a porous carbon matrix (abbreviated as Sn@C). Sn@C exhibited remarkably high electrochemical lithium stability (tested over 100 charge and discharge cycles) and high specific capacities over a wide range of operating currents (0.2-5 Ag-1). The novel synthesis strategy to obtain Sn@C from a single precursor as discussed herein provides an optimal combination of particle size and dispersion for buffering severe volume changes due to Li-Sn alloying reaction and provides fast pathways for lithium and electron transport.

Porous lithium rich Li1.2Mn0.54Ni0.22Fe0.04O2 prepared by microemulsion route as a high capacity and high rate capability positive electrode material

A porous layered composite of Li2MnO3 and LiMn0.35Ni0.55Fe0.1O2 (composition:Li1.2Mn0.54Ni0.22Fe0.04O2) is prepared by inverse microemulsion method and studied as a positive electrode material. The precursor is heated at several temperatures between 500 and 900 degrees C. The X-ray diffraction, scanning electron microscopy, and transmission electron microscopy studies suggested that well crystalline submicronsized particles are obtained. The product samples possess mesoporosity with broadly distributed pores around 10 similar to 50 nm diameter. Pore volume and surface area decrease by increasing the temperature of preparation. However, the electrochemical activity of the composite samples increases with an increase in temperature. The discharge capacity values of the samples prepared at 900 degrees C are about 186 mAh g(-1) at a specific current of 25 mA g(-1) with an excellent cycling stability. The composite sample also possesses high rate capability. The high rate capability is attributed to the porous nature of the material. (C) 2014 Elsevier Ltd. All rights reserved.

Hydrogen bonding, halogen bonding and lithium bonding: an atoms in molecules and natural bond orbital perspective towards conservation of total bond order, inter- and intra-molecular bonding

One hundred complexes have been investigated exhibiting D-X center dot center dot center dot A interactions, where X = H, Cl or Li and DX is the `X bond' donor and A is the acceptor. The optimized structures of all these complexes have been used to propose a generalized `Legon-Millen rule' for the angular geometry in all these interactions. A detailed Atoms in Molecules (AIM) theoretical analysis confirms an important conclusion, known in the literature: there is a strong correlation between the electron density at the X center dot center dot center dot A bond critical point (BCP) and the interaction energy for all these interactions. In addition, we show that extrapolation of the fitted line leads to the ionic bond for Li-bonding (electrostatic) while for hydrogen and chlorine bonding, it leads to the covalent bond. Further, we observe a strong correlation between the change in electron density at the D-X BCP and that at the X center dot center dot center dot A BCP, suggesting conservation of the bond order. The correlation found between penetration and electron density at BCP can be very useful for crystal structure analysis, which relies on arbitrary van der Waals radii for estimating penetration. Various criteria proposed for shared-and closed-shell interactions based on electron density topology have been tested for H/Cl/Li bonded complexes. Finally, using the natural bond orbital (NBO) analysis it is shown that the D-X bond weakens upon X bond formation, whether it is ionic (DLi) or covalent (DH/DCl) and the respective indices such as ionicity or covalent bond order decrease. Clearly, one can think of conservation of bond order that includes ionic and covalent contributions to both D-X and X center dot center dot center dot A bonds, for not only X = H/Cl/Li investigated here but also any atom involved in intermolecular bonding.

Multi-component Olivine for Lithium-Ion Hybrid Capacitor

A lithium-ion hybrid capacitor comprising of a battery type multi-component olivine (LiMn1/3Co1/3Ni1/3PO4) cathode and a capacitive type carbon negative electrode is reported. Olivine phosphate synthesized with chelating agent's polyvinylpyrrolidone (PVP) or triethanolamine (TEA) showed uniform carbon coating through in-situ process exhibiting a surface area 5.1 m(2)/g with porosity 0.02 cm(3)/g. The surface area for commercial carbon electrode was observed to be 1450 m(2)/g with high porosity 0.76 cm(3)/g. Galvanostatic charge/discharge cycling tests were conducted in the coin cells, olivine vs. Li, offering a cell voltage of 4.75 V vs. Li with a maximum specific capacitance of 125 F/g. In the case of olivine vs. carbon in a lithium-ion hybrid device delivered a high discharge capacitance of 86 F/g at a specific current of 0.12 A/g with a cycling retention of 53 F/g (38% loss) after 250 cycles. The obtained performance of PVP synthesized olivine material is manifested to uniform carbon coating and the trapped organic products that provide pathways for facile electrochemical reactions than their TEA counterparts.

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 M = Mn, Fe)

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R (3) over barm) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn3+ and low spin configuration for Ru4+ where the itinerant electrons occupy a pi*-band. The onset of a net maximum in the chi vs. T plot at 9.5 K and the negative value of the Weiss constant (theta) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn3+ and Ru4+ are partially oxidized to Mn4+ and Ru5+ in the sloping region at low voltage, while in the long plateau, O2- is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O2- ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O2- (plateau) while Fe seems to retain its 3+ state.

An alluaudite Na-2+Fe-2x(2-x)(SO4)(3)(x=0.2) derivative phase as insertion host for lithium battery

A new desodiated derivative compound, Na0.89Fe1.8(SO4)(3), was prepared by the chemical oxidation of alluaudite Na2.4Fe1.8(SO4)(3) Phase using NOBF4 as oxidant. The structure and valency of Fe were characterized by X-ray diffraction (XRD) and Fe-57 Mossbauer spectroscopy. Intercalation behavior of lithium ions in the structure of Na0.89Fe1.8(SO4)(3) was gauged by electrochemical analyses and ex-situ X-ray diffraction. A high capacity of 110 mAh g(-1) at 0.1 C was obtained with a good rate kinetics within a range of 0.1-10 C(1 C = 118 mAh g-1) involving a high Fe3+/Fe2+ redox potential of 3.75 V (vs. Li/Li+). These results confirmed that the Na2.4-delta Fe1.8(SO4)(3) framework was stable even after oxidation and forms a new competitive cathode for the reversible intercalation of lithium ions. (C) 2014 Elsevier B.V. All rights reserved.

Porous Flower-like alpha-Fe2O3 Nanostructure: A High Performance Anode Material for Lithium-ion Batteries

Porous flower-like alpha-Fe2O3 nanostructures have been synthesized by ethylene glycol mediated iron alkoxide as an intermediate and studied as an anode material of Li-ion battery. The iron alkoxide precursor is heated at different temperatures from 300 to 700 degrees C. The alpha-Fe2O3 samples possess porosity and high surface area. There is a decrease in pore volume as well as surface area by increasing the preparation temperature. The reversible cycling properties of the alpha-Fe2O3 nanostructures have been evaluated by cyclic voltammetry, galvanostatic charge discharge cycling, and galvanostatic intermittent titration measurements at ambient temperature. The initial discharge capacity values of 1063, 1168,1183, 1152 and 968 mAh g(-1) at a specific current of 50 mA g(-1) are obtained for the samples prepared at 300, 400, 500, 600 and 700 degrees C, respectively. The samples prepared at 500 and 600 degrees C exhibit good cycling performance with high rate capability. The high rate capacity is attributed to porous nature of the materials. As the iron oxides are inexpensive and environmental friendly, the alpha-Fe2O3 has potential application as anode material for rechargeable Li batteries. (C) 2015 Elsevier Ltd. All rights reserved.

Early postnatal exposure to lithium in vitro induces changes in AMPAR mEPSCs and vesicular recycling at hippocampal glutamatergic synapses

Lithium is an effective mood stabilizer but its use is associated with many side effects. Electrophysiological recordings of miniature excitatory postsynaptic currents (mEPSCs) mediated by glutamate receptor AMPA-subtype (AMPARs) in hippocampal pyramidal neurons revealed that CLi (therapeutic concentration of 1 mM lithium, from days in vitro 4-10) decreased the mean amplitude and mean rectification index (RI) of AMPAR mEPSCs. Lowered mean RI indicate that contribution of Ca2+-permeable AMPARs in synaptic events is higher in CLi neurons (supported by experiments sensitive to Ca2+-permeable AMPAR modulation). Co-inhibiting PKA, GSK-3 beta and glutamate reuptake was necessary to bring about changes in AMPAR mEPSCs similar to that seen in CLi neurons. FM1-43 experiments revealed that recycling pool size was affected in CLi cultures. Results from minimum loading, chlorpromazine treatment and hyperosmotic treatment experiments indicate that endocytosis in CLi is affected while not much difference is seen in modes of exocytosis. CLi cultures did not show the high KCl associated presynaptic potentiation observed in control cultures. This study, by calling attention to long-term lithium-exposure-induced synaptic changes, might have implications in understanding the side effects such as CNS complications occurring in perinatally exposed babies and cognitive dulling seen in patients on lithium treatment.