Electronic structure for sliding charge density waves

We present a model for the electron system in NbSe₃ based on its quasi one-dimensional metallic properties. In a one-dimensional metal phonon drag of 2K_F-phonons takes place at temperatures higher than θ_D, since the phonon-electron scattering rate τ^?1_ph?el is greater than the phonon-phonon rate τ^?1_ph?ph. this situation is in contrast to the situation in three dimensional metals, where phonon drag takes place only at very low temperatures. Our model explains the transport properties of the material including the electrical conductivity anistropy, the conductivity in a strong electric field, and the Hall effect data.     

Diamondlike nanocomposite a-C:H:Cr Coatings: Structure,mechanical, and tribological properties

The results from a comprehensive investigation of the structure, phase and chemical composition, microhardness, and nanomechanical and tribological properties of chromium-doped coatings of hydrogenised amorphous carbon a-C:H:Cr are presented. The coatings are deposited via reactive magnetron sputtering in an Ar + C₂H₂ + N₂ gas mixture at various volume concentrations of nitrogen and acetylene. It is found that the carbon in the coatings is formed as disordered mixtures of domains with tetrahedral (sp ³) and hexagonal (sp ²) carbon coordinations. In addition, the doping metal in the coating consists of nanosized inclusions of metallic chromium and its carbide and nitride phases. Additional nitrogen doping resulting in the formation of chromium nitride is shown to improve the micromechanical and tribological properties of the obtained coatings.     

Clustering and polymerization of Li15C60

The structural and electronic properties of lithium intercalated fullerides (of which Li₁₅C₆₀ is the most representative) are still puzzling and unclear. Above 520 K, x-ray/neutron diffraction shows an fcc phase in which the 15 Li atoms clusterize in the octahedral interstices. However, at lower temperatures, a change in the crystalline symmetry and also in the electronic properties takes place as observed from ¹³C, ⁷Li/⁶Li NMR and x-ray diffraction measurements. X-ray diffraction data suggest the presence of two different stable structures: a tetragonal monomeric and an orthorhombic polymerised phase. Detailed ¹³C magic angle spinning NMR experiments in the latter phase indicate sp ³ bondings among the carbon atoms, whereas the relative (sp ²/sp ³) intensities, together with x-ray data, suggest the C₆₀ polymerization to be a [2+2] cycloaddition. Multiple quantum NMR experiments on ⁷Li confirm the presence of lithium clusters, as observed by x-ray diffraction in the high temperature phase, also at lower temperatures. However, the inferred cluster size is significantly smaller than that suggested by the stoichiometry. The distortion in the low-T structure of L₁₅C₆₀ is supposed to induce the migration of Li atoms from octahedral to tetrahedral voids, thus accounting for the lower number of Li atoms in the clusters. Further evidence of this scenario is obtained also from preliminary measurements of line shapes and T ₁ relaxation times, which exhibit a multiexponential recovery with very different constants that are hardly compatible with a single family of Li atom sites.     

Formation of carbon-encapsulated metallic nano-particles from metal acetylides by electron beam irradiation

Transition metal acetylides, MC₂ (M=Fe, Co and Ni), exhibit ferromagnetic behavior of which T_C is characteristic of their size and structure. CoC₂ synthesized in anhydrous condition exhibited cubic structure with disordered C₂^2- orientation. Once being exposed to water (or air), the particles behave ferromagnetically due to the lengthening of the Co–Co distance by the coordination of water molecules to Co²⁺ cations. Heating of these particles induces segregation of metallic cores with carbon mantles. Electron beam or 193 nm laser beam can produce nanoparticles with metallic cores covered with carbon mantles.     

NMR relaxation rate in metallic carbon nanotubes

NMR relaxation rate, T₁⁻¹, of the metallic carbon nanotube is discussed based on Tomonaga–Luttinger-liquid theory. It is found that the Coulomb interaction leads to increase of (T₁T)⁻¹ by a power law with decreasing temperature, T. The dependence on temperature of (T₁T)⁻¹ in the multi-wall nanotube (MWNT) is shown to be strongly suppressed by existence of the metallic shells in the MWNTs.     

Microscopic magnetic properties of (V1−xTix)2O3 near the phase boundary of the metal–insulator transition

Magnetic susceptibility (χ) and ⁵¹V NMR have been measured in (V_1−xTi_x)₂O₃ near the phase boundary of the metal–insulator transition. It is established that the transition from antiferromagnetic insulating (AFI) to antiferromagnetic metallic phases near x_c≈0.05 is not quantum critical, but is discontinuous with a jump of the transition temperature. In the AFI phase at 4.2 K, we observed the satellite in the zero-field ⁵¹V NMR spectrum around 181 MHz in addition to the ‘host’ resonance around 203 MHz. The satellite is also observable in the paramagnetic metallic phase of the x=0.055 sample. We associated the satellite with the V sites near Ti, which are in the V³⁺-like oxidation state, but has different temperature dependence of the NMR shift from that of the host V site. The host d-spin susceptibility for x=0.055 decreases below ∼60 K, but remains finite in the low-temperature limit.     

Raman light scattering in hydrogenated metal-carbon composite films

We have used Raman scattering, elemental analysis, and structural analysis to study the effect of the concentration of incorporated metals (Cu, Ni) on the ratio of sp²/sp³ carbon bonds in composite hydrogen-containing films a-C:H/Cu and a-C:H/Ni, formed by combining plasma-enhanced vapor phase deposition of carbon and sputtering of the metal, using a mixture of argon and methane or acetylene gases. We have shown that formation of a nanosized structure of metallic crystallites (2–5 nm) in the composite films leads to a significant increase in the fraction of disordered sp³-bonded carbon clusters and a decrease in the linear dimensions of the graphite-like carbon clusters. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 344–348, May–June, 2006.     

Lithium ion diffusion in LixNiPS3 single crystals

Electrochemical studies have been made of the kinetics and thermodynamics of lithium intercalation into single crystals of NiPS₃. Effective diffusion coefficients for lithium in this layered compound were found to be higher than previously reported for powdered NiPS₃ cathodes, and very much higher than expected from previous nmr studies. Despite considerable electron transfer in Li⁺_xNiPS^x-₃, the electronic conductivity does not approach metallic values until x 1.4. The transition to a previously described state of high ionic conductivity is discussed.     

X-ray study of metal oxide based anodes for Li-ion batteries

Cells were made from Co₃O₄ and Co₂SnO₄ and lithium metal and tested to determine reversible lithium capacity. Li is reversibly inserted into Co₃O₄, as was observed by electrochemistry, coupled with changes of cobalt oxidation state as observed by Co K-edge EXAFS. On lithium insertion the Co₃O₄ is reduced to yield only metallic cobalt species, and then on lithium removal an oxide of Co is formed. The EXAFS data further showed that the initial reduction was to Co(II) and then to metallic Co, and that both the metallic and oxide phases were disordered, having low co-ordination numbers and large shell spacings. The electrochemical behaviour of the Co₂SnO₄ cells was closer to that of SnO₂ than Co₃O₄, but did exhibit changes obviously caused by the cobalt. EXAFS on Co₂SnO₄ cells revealed that the Co is reduced to metallic cobalt on the initial discharge, but does not convert back to an oxide on cycling. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

6,7Li NMR study of ion mobility on the molecular scale in lithated imidazole complexes

Two model compounds, lithium imidazolium (LiIm) and lithium 2-undecylimidazolium (und-LiIm), were synthesized. These materials are chosen as models of potential lithium ion conductors for use as electrolytes in lithium batteries. Solid-state NMR was used to provide information on the microscopic interactions including ionic mobility and ring reorientations which govern the efficiency of conductivity. Lithium imidazolium was mixed with lithium methylsulfonate, generating a doped complex in which a doubly lithiated imidazole ring was inferred based on the ⁷Li NMR chemical shifts. Our research includes ^6,7Li variable temperature MAS NMR experiments at intermediate spinning speeds, relaxation studies to determine spin-lattice relaxation times (T₁) of lithium ion hopping, and 2D exchange spectroscopy to determine possible chemical exchange processes. The possibility of 2-site ring reorientation for the doubly lithiated imidazole ring was supported by exchange spectroscopy. Comparisons of spin-lattice relaxation times and corresponding activation energies of the lithium imidazolium and the doped complex point to a higher degree of mobility in the latter.Lithium 2-undecylimidazolium was prepared and exhibited a lower melting point than the parent lithium imidazolium, as expected. This small molecule was chosen as representative of a side-chain functionalized polyethylene-based material. ⁷Li MAS spectra show mainly the presence of the doubly lithiated imidazole ring in pure und-LiIm, and in the LiCH₃SO₃–und-LiIm mixture. The data clearly indicate local mobility of the lithium ions in the materials.     

Lithium insertion into nanometer-sized rutile-type TixSn1 − xO2 solid solutions

The electrochemical properties of rutile-type Ti_xSn_1?xO₂ solid solutions (x = 0–1.0) as an anode for a lithium–ion battery were investigated using nanosized crystals prepared by an aqueous solution process. The reduction of the crystal size to nanoscale allowed a smooth lithium insertion into the rutile framework at room temperature. The lithium-insertion behavior of TiO₂, SnO₂, and the solid solutions was evaluated without any structural change of the rutile-type crystal structure in the potential range of 1.2–3.5 V (versus Li/Li⁺). The interstitial spaces for lithium ions were found to be derived from the crystal structure of the rutile framework and independent of the metal species.     

Structural Nature of 7Li and 11B Sites by Static NMR and MAS NMR in Nonlinear Optical Material LiCsB6O10

The relationship between structure and nonlinear optical properties in LiCsB₆O₁₀ is characterized using single-crystal nuclear magnetic resonance (NMR) and magic-angle spinning (MAS) NMR. Although the quadrupole parameters for B(1) and B(2) sites were obtained using single-crystal NMR, the T ₁ values for these atomic sites could not be distinguished in this way. Thus, the structural nature of lithium and boron sites in LiCsB₆O₁₀ was investigated using MAS NMR. B(1) and B(2) sites could be distinguished based on the spectrum and T _1ρ obtained from ¹¹B MAS NMR. In addition, the T ₁ and T _1ρ values and activation energies for ⁷Li and ¹¹B are compared. No significant changes were seen in the T _1ρ at the lithium and boron nuclei in LiCsB₆O₁₀.     

Preparation and characterization of LiTi<Subscript>2</Subscript>O<Subscript>4</Subscript> anode material synthesized by one-step solid-state reaction

LiTi₂O₄ anode material for lithium-ion battery has been prepared by a novel one-step solid-state reaction method using Li₂CO₃, TiO₂, and carbon black as raw materials. X-ray diffraction, scanning electron microscopy, energy-dispersive spectrometry, and the determination of electrochemical properties show that the single phase of LiTi₂O₄ with spinel crystal structure is formed at 850?°C by this new method, and the lattice parameter is about 8.392?Å. The primary particle size of the LiTi₂O₄ powder is about 0.5–1.0 μm and its morphology is similar to a sphere. The lithium ion insertion voltage of LiTi₂O₄ anode material is about 1.50 V versus lithium metal, the initial discharge capacity is about 133.6 mAh g^-1, the charge–discharge voltage plateau is very flat, and no solid electrolyte interface film is formed when working potential is more than 1.0 V. The reaction reversibility and the cycling stability are excellent, and the high rate performance is good.     

Eggshell‐Assisted Preparation of Mixed Nanoparticles Simultaneously Encapsulated in Carbon Microcubes for Reversible Lithium Storage

Nanoparticle‐based electrodes often suffer from poor electrical properties due to high interparticle resistance, as well as low Coulombic efficiency attributed to large surface area induced parasitic reactions. In order to address this issue, a strategy of encapsulating two kinds of nanoparticles of both metal oxide and metallic nanoparticles is attempted, simultaneously, in microscale carbon cubic shells for highly reversible lithium storage. The unique structure is synthesized by simultaneous reactions of (1) decomposition of crystalline Co₂(OH)₃Cl microparticle precursor, synthesized in unique eggshell reactor systems, into nanoparticles, (2) partial reduction of CoO into metallic Co by eggshell membrane, (3) carbon coating by chemical vapor deposition facilitated by presence of catalytic Co with carbon released from the eggshell membrane, and (4) microscale carbon shell formed using the Co₂(OH)₃Cl particles as microtemplates. The carbon shells can prevent the encapsulated mixed nanoparticles from direct contact with electrolyte and reduce undesirable parasitic reactions, and accommodate volumetric variation during cycling. The introduction of metallic Co nanoparticles can reduce interparticle resistance. When evaluated for lithium storage, the unique structures of CoO–Co@C demonstrate superior electrochemical performances in terms of electrode stability and rate performance, as compared to that of pure CoO.     

Synthesis and physicochemical properties of Li2 Me x Zr1 − x O3 − δ (Me = Nb,Ti; x = 0.05, 0.1) solid solutions

Complex lithium metallates Li₂ Me _x Zr_{1 ? x} O_{3 ? δ} (Me = Nb, Ti, x = 0.05, 0.1) with iso-and heterovalent substitutions for Zr⁴⁺ ions in lithium zirconate are synthesized for the first time using a citrate technique. The inclusion of Ti⁴⁺ and Nb⁵⁺ ions in the crystal structure of Li₂ZrO₃ is confirmed by means of X-ray diffraction and NMR. It is shown that in the temperature range of 750–820 K, Li₂Ti_0.1Zr_0.9O₃ solid solution has higher conductivity than phases of undoped lithium zirconate.     

Quadrupole interactions in lithium borodeuteride

Polycrystalline samples of lithium borohydride and borodeuteride, LiBH₄ and LiBD₄, are studied by ²H, ⁷Li, and ^10,11B NMR in 7.04 T and 9.35 T magnetic fields in the temperature range 116–580 K. The ^10,11B NMR line shape of the orthorhombic phase of LiBH₄ and LiBD₄ suggests that first-order quadrupole interaction takes place. The quadrupole coupling constant (QCC) χ _q and asymmetry parameter η of the electric field gradient tensor for ¹¹B are described by linear temperature dependences: χ _q (¹¹B) = 177 ? 0.24T and η = 0.043 + 0.0014T. The electric field gradient at the positions of boron nuclei is created by external charges, primarily lithium cations. In the range of 388–391 K, the ⁷Li NMR line shape reflects the coexistence of two phase modifications of LiBH₄ and LiBD₄ and the occurrence of a reversible first-order phase transition. In the temperature range of 390–530 K, the ⁷Li NMR line shape represents a first-order quadrupole perturbed spectrum with zero asymmetry parameter and a weakly temperature dependent ⁷Li QCC. The spin-lattice relaxation time and the NMR line shape of ²H are interpreted in terms of the reorientation of the BD ₄ ^? anion about their proper symmetry axes C₂ and C₃.     

Synthesis and characterization of SWNT-heavy alkali metal intercalation compounds,effect of host SWNTs materials

Singlewall carbon nanotubes (SWNTs) produced by electric-arc and laser ablation methods were characterized by X-ray diffraction before and after the reaction with alkali metals (M=K, Rb, and Cs). Reaction with annealed SWNTs gave MC₈ composition at saturation. The alkali metal lattice showed short range order incommensurate with graphene cylinders of SWNTs. X-ray diffractogram simulations have enabled the study of the influence of SWNTs structure on that of intercalation compounds. Chemically-purified bundles, constituted of open SWNTs, can be intercalated inside and between the tubes forming disordered structures. Annealed or pristine bundles were intercalated only between the tubes leading to short or long range ordered structure depending on host crystallinity and alkali metal (K, Rb or Cs). The expansion of the 2D SWNTs lattice after intercalation is comparable to graphite intercalation compounds. Some 2D arrangements of SWNTs and K atoms are proposed and discussed to reproduce XRD results. ¹³C NMR and ESR studies of annealed doped SWNTs emphasize the fact that the intercalation compounds of SWNTs are metallic.     

Thermodynamic approach to the size dependence of the melting temperatures of films

The size dependence of melting temperature T _m of metallic films (tin and copper) on different substrates, including amorphous carbon and another refractory metal (i.e., the dependence of T _m on film thickness h) is investigated. It is found that the effect of the interfacial boundary can result in the growth of T _m for thin metallic films on carbon substrates with a reduction in film thickness h. For a system with a metallic film on a metallic substrate, the size dependence of T _m is less pronounced and T _m falls with a reduction in h.     

VSe2−xSx materials as battery cathode

The properties of the solid solution VSe_2?xS_x 0 ? x_nom ? 2 have been investigated for secondary battery application. The phase VSe₂ is observed for 0 ? x_nom ? 1.2 and the phase V₅S₈ is found using RX analysis for x_nom >1.2. The amount of lithium chemically incorporated in this structure by reaction with n-butyllithium is 2 Li/vanadium for 0 ? x_nom ? 0.8 and 1.4 Li/vanadium for V₅S₈. An electrochemical technique (galvanostatic) indicates that the amount of lithium incorporated depends on the x_nom values, the grain size and the discharge rate. The best results are obtained for 0.2 ? x_nom ? 0.6 (capacity = 164?172 Ah kg^?1 and energy density = 385?465 Wh kg^?1).     

Microscopic magnetic properties of nonstoichiometric V2O3+x—NMR and inelastic spin-flip neutron scattering measurements

The local magnetic properties of the V sites in the nonstoichiometric V₂O_3+x (0 ? x <0.08) have been examined by nuclear magnetic resonance and inelastic spin-flip neutron scattering techniques. The samples with x = 0.01 and 0.02 show a paramagnetic metal (PM)-antiferromagnetic insulator (AFI) transition. In the AFI phase, two distinct ⁵¹V NMR signals with hyperfine fields H_n = 184.9±0.5 kOe and 71±1 kOe were observed at 1.8 K, which were assigned as due to V³⁺ and V³⁺ sites, respectively. On the other hand, the samples with x = 0.04 and 0.06 were metallic down to 1.4K, and showed a paramagnetic (PM)-antiferromagnetic (AFM) transition at about 10 K. In these samples, a ⁵¹V NMR signal with H_n = 58±2 k0e and one with 〈H_n〉 = 9kOe were observed at 1.8 K, which were assigned as due to V³⁺-like sites and the matrix V sites, respectively. These results are entirely consistent with those obtained from the neutron experiment. We propose that in the metallic phase (0.04 ? x < 0.08) the minority V⁴⁺-like sites are magnetically localized in the delocalized V matrix and may be responsible for the antiferromagnetic long range order below 10 K.