(De)lithiation mechanism of Li/SeS(x) (x = 0-7) batteries determined by in situ synchrotron X-ray diffraction and X-ray absorption spectroscopy.

Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.

Sodium Rich Vanadium Oxy-Fluorophosphate - Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O - as Advanced Cathode for Sodium Ion Batteries.

Conventional sodium-based layered oxide cathodes are extremely air sensitive and possess poor electrochemical performance along with safety concerns when operating at high voltage. The polyanion phosphate, Na3 V2 (PO4 )3 stands out as an excellent candidate due to its high nominal voltage, ambient air stability, and long cycle life. The caveat is that Na3 V2 (PO4 )3 can only exhibit reversible capacities in the range of 100 mAh g-1 , 20% below its theoretical capacity. Here, the synthesis and characterizations are reported for the first time of the sodium-rich vanadium oxyfluorophosphate, Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O, a tailored derivative compound of Na3 V2 (PO4 )3 , with extensive electrochemical and structural analyses. Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O delivers an initial reversible capacity of 117 mAh g-1 between 2.5 and 4.5 V under the 1C rate at room temperature, with 85% capacity retention after 900 cycles. The cycling stability is further improved when the material is cycled at 50 °C within 2.8-4.3 V for 100 cycles. When paired with a presodiated hard carbon, Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O cycled with a capacity retention of 85% after 500 cycles. Cosubstitution of the transition metal and fluorine in Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O as well as the sodium-rich structure are the major factors behind the improvement of specific capacity and cycling stability, which paves the way for this cathode in sodium-ion batteries.

A new class of lithium and sodium rechargeable batteries based on selenium and selenium-sulfur as a positive electrode.

A new class of selenium and selenium-sulfur (Se(x)S(y))-based cathode materials for room temperature lithium and sodium batteries is reported. The structural mechanisms for Li/Na insertion in these electrodes were investigated using pair distribution function (PDF) analysis. Not only does the Se electrode show promising electrochemical performance with both Li and Na anodes, but the additional potential for mixed Se(x)S(y) systems allows for tunable electrodes, combining the high capacities of S-rich systems with the high electrical conductivity of the d-electron containing Se. Unlike the widely studied Li/S system, both Se and Se(x)S(y) can be cycled to high voltages (up to 4.6 V) without failure. Their high densities and voltage output offer greater volumetric energy densities than S-based batteries, opening possibilities for new energy storage systems that can enable electric vehicles and smart grids.

Exfoliation and reassembly of cobalt oxide nanosheets into a reversible lithium-ion battery cathode.

An exfoliation-reassembly-activation (ERA) approach to lithium-ion battery cathode fabrication is introduced, demonstrating that inactive HCoO(2) powder can be converted into a reversible Li(1-x) H(x) CoO(2) thin-film cathode. This strategy circumvents the inherent difficulties often associated with the powder processing of the layered solids typically employed as cathode materials. The delamination of HCoO(2) via a combination of chemical and mechanical exfoliation generates a highly processable aqueous dispersion of [CoO(2) ](-) nanosheets that is critical to the ERA approach. Following vacuum-assisted self-assembly to yield a thin-film cathode and ion exchange to activate this material, the generated cathodes exhibit excellent cyclability and discharge capacities approaching that of low-temperature-prepared LiCoO(2) (~83 mAh g(-1) ), with this good electrochemical performance attributable to the high degree of order in the reassembled cathode.

Temperature-dependent Battery Performance of a Na3 V2 (PO4 )2 F3 @MWCNT Cathode and In-situ Heat Generation on Cycling.

Excellent structural stability, high operating voltage, and high capacity have made Na3 V2 (PO4 )2 F3 a promising cathode material for sodium-ion batteries. However, high-temperature battery performances and heat generation measurements have not been systematically reported yet. Carbon-coated Na3 V2 (PO4 )2 F3 @MWCNT (multi-walled carbon nanotube) samples are fabricated by a hydrothermal-assisted sol-gel method and the electrochemical performances are evaluated at three different temperatures (25, 45, and 55 °C). The well-crystallized Na3 V2 (PO4 )2 F3 @MWCNT samples exhibit good cycling stability at both low and high temperatures; they deliver an initial discharge capacity of 120-125 mAhg-1 at a 1 C rate with a retention of 53 % capacity after 1,400 cycles with 99 % columbic efficiency. The half-cell delivers a capacity of 100 mAhg-1 even at a high rate of 10 C at room temperature. Furthermore, the Na3 V2 (PO4 )2 F3 @MWCNT samples show good long-term durability; the capacity loss is an average of 0.05 % per cycle at a 1 C rate at 55 °C. Furthermore, ionic diffusivity and charge transfer resistance are evaluated as functions of state of charge, and they explain the high electrochemical performance of the Na3 V2 (PO4 )2 F3 @MWCNT samples. In-situ heat generation measurements reveal reversible results upon cycling owing to the high structural stability of the material. Excellent electrochemical performances are also demonstrated in the full-cell configuration with hard carbon as well as antimony Sb/C anodes.

Nanocolumnar structured porous Cu-Sn thin film as anode material for lithium-ion batteries.

Two nanocolumnar structured porous Cu-Sn films were produced by tuning the duration of the process using an oblique angle deposition (OAD) technique of electron beam coevaporation method. The structural and morphological properties of these porous Cu-Sn films are characterized using thin film X-ray diffraction, scanning electron microcopy (SEM) and atomic force microscopy (AFM). Galvanostatic half-cell electrochemical measurements were conducted in between 5 mV to 2.5 V using a Li counter electrode, demonstrating that the Cu rich Cu6Sn5 thin film having homogenously distributed nanocolumns achieved a good cycleability up to 100 cycles with a high capacity retention, whereas the Cu6Sn5 nanostructured porous thick film with inhomogeneous morphology showed only a very short cycle life (<25 cycles).The difference in the electrochemical performances of the thin and thick nanocolumnar structured porous Cu-Sn films resulting from different evaporation duration was evaluated on the basis of X-ray photoelectron spectroscopy (XPS) analysis on the cycled samples.

Li-Se battery: absence of lithium polyselenides in carbonate based electrolyte.

The lithiation mechanism of the Li-Se cell in a carbonate-based electrolyte is discussed. It is found that Se is directly reduced to Li2Se in discharge without intermediate phases detected by in situ X-ray diffraction or X-ray absorption spectroscopy. The reason is that the redox products Se and Li2Se, as well as lithium polyselenides are insoluble in the electrolyte.

Chemically active reduced graphene oxide with tunable C/O ratios.

Organic dispersions of graphene oxide can be thermally reduced in polar organic solvents under reflux conditions to afford electrically conductive, chemically active reduced graphene oxide (CARGO) with tunable C/O ratios, dependent on the boiling point of the solvent. The reductions are achieved after only 1 h of reflux, and the corresponding C/O ratios do not change upon further thermal treatment. Hydroxyl and carboxyl groups can be removed when the reflux is carried out above 155 °C, while epoxides are removable only when the temperature is higher than 200 °C. The increasing hydrophobic nature of CARGO, as its C/O ratio increases, improves the dispersibility of the nanosheets in a polystyrene matrix, in contrast to the aggregates formed with CARGO having lower C/O ratios. The excellent processability of the obtained CARGO dispersions is demonstrated via free-standing CARGO papers that exhibit tunable electrical conductivity/chemical activity and can be used as lithium-ion battery anodes with enhanced Coulombic efficiency.

The plastic-crystalline phase of succinonitrile as a universal matrix for solid-state ionic conductors.

Solid ionic conductors are actively sought for their potential application in electrochemical devices, particularly lithium batteries. We have found high ionic conductivity for a large variety of salts dissolved in the highly polar medium based on the plastic-crystal form of succinonitrile (N[triple bond]C[bond]CH(2)[bond]CH(2)[bond]C[triple bond]N). Its high diffusivity, plasticity and solvating power allowed the preparation of a large number of materials with high ionic conductivity, reaching values of 3 mS cm(-1) at 25 degrees C (two orders of magnitude above polymers). Their ease of preparation and processing allowed us to study the influence of the solute on ionic conduction within this medium. Comparisons revealed a dichotomy between plastic crystals and conventional polymer media. The usefulness of these new, easily processed electrolytes was asserted in electrochemical tests with lithium intercalation electrodes.