The Raman spectra of (1 − x)(BMITFSI), xLiTFSI ionic liquids, where 1-butyl-3-methylimidazolium cation (BMI + ) and bis(trifluoromethane-sulfonyl)imide anion (TFSI − ) are analyzed for LiTFSI mole fractions x < 0.4. As expected from previous studies on similar TFSI-based systems, most lithium ions are shown to be coordinated within [Li(TFSI) 2 ] − anionic clusters. The variation of the self-diffusion coefficients of the 1 H, 19 F, and 7 Li nuclei, measured by pulsed-gradient spin-echo NMR (PGSE-NMR) as a function of x, can be rationalized in terms of the weighted contribution of BMI + cations, TFSI − 'free' anions, and [Li(TFSI) 2 ] − anionic clusters. This implies a negative transference number for lithium.

Electrochemical capacity retention of nearly X-ray amorphous nanostructured manganese oxide (nanoMnO 2 ) synthesized by mixing directly KMnO 4 with ethylene glycol under ambient conditions for supercapacitor studies is enhanced significantly. Although X-ray diffraction (XRD) pattern of nanoMnO 2 shows poor crystallinity, it is found that by Mn K-edge X-ray absorption near edge structure (XANES) measurement that the nanoMnO 2 obtained is locally arranged in a δ-MnO 2 -type layered structure composed of edge-shared network of MnO 6 octahedra. Field emission scanning electron microscopy and XANES measurements show that nanoMnO 2 contains nearly spherical shaped morphology with δ-MnO 2 structure, and 1D nanorods of R-MnO 2 type structure (powder XRD) in the annealed (600 °C) sample. Volumetric nitrogen adsorption-desorption isotherms, inductively coupled plasma analysis, and thermal analysis are carried out to obtain physicochemical properties such as surface area (230 m 2 g -1 ), porosity of nanoMnO 2 (secondary mesopores of diameter 14.5 nm), water content, composition, etc., which lead to the promising electrochemical properties as an electrode for supercapacitor. The nanoMnO 2 shows a very high stability even after 1200 cycles with capacity retention of about 250 F g -1 .

Systematic Mn 2p XPS and Mn K-edge XAS analyses together with the electrochemical measurement have been carried out for the spinel LiMn 2 O 4 prepared at various sintering temperatures in order to elucidate an origin of the dependence of electrochemical properties on synthetic conditions. From the comparative experiments, it becomes clear that a lowering of synthetic temperature gives rise to an increase of structural disorder and of the average oxidation state of manganese, which is more prominent on the surface than in the bulk. Such results suggest that the modification of surface property induced by a decrease of particle size is closely related to the electrochemical performance. The nanocrystalline LiMn 2 O 4 prepared at 250 °C shows excellent cyclability at the 3 V region compared to that of microcrystalline LiMn 2 O 4 prepared at 700 °C. For the purpose of examining the evolution of the chemical bonding nature of inserted lithium, 7 Li MAS NMR studies have been performed for both the spinel compounds before and after Li + intercalation. While the intercalation of 0.2 mol Li + does not induce any remarkable spectral change for the microcrystalline LiMn 2 O 4 , it leads to a dramatic suppression of the NMR signal for the nanocrystalline LiMn 2 O 4 , indicating that the process of grafting Li into the latter phase results in significant modifications of the chemical environment of lithium. On the basis of present experimental findings, it can be concluded that the lowering of synthetic temperature modifies the surface properties, which facilitates the grafting process of Li + ion and, thereby, enhances the electrochemical properties for the 3 V region corresponding to the Li insertion.

Mn K-edge X-ray absorption spectroscopic (XAS) analyses have been performed to probe the evolution of electronic and crystal structures of layered LiMnO2 upon chemical and electrochemical delithiation/relithiation. According to the X-ray absorption near-edge structure studies, it becomes clear that the trivalent manganese ion in LiMnO2 is significantly oxidized by acid treatment and is not fully recovered by subsequent lithiation reaction with n-BuLi. The extended X-ray absorption fine structure results presented here demonstrate that the local structure around manganese in LiMnO2 is changed from a layered α-NaFeO2-type structure to a spinel-like one upon chemical delithiation reaction. It is also found from the XAS analyses for the cycled LiMnO2 that the electrochemical charge−discharge process gives rise not only to the partial oxidation of manganese ion but also to the migration of Mn into the interlayer lithium site, resulting in the coexistence of the layered structure and the spinel one. Such results highlight the lattice instability of layered manganese oxide for the chemical and electrochemical extraction of lithium, which is responsible for the remarkable capacity fading and the formation of two plateaus at around the 3 and 4 V regions after the first electrochemical cycle. On the basis of the present experimental findings, we are now able to suggest that the electrochemical performance of layered LiMnO2 can be improved by blocking the Mn migration path through cationic substitution.

No abstract

A new nanocrystalline potassium-based lithium manganese oxyiodide has been prepared by using Chimie Douce route at room temperature. According to the electrochemical measurements, this nanocrystalline sample shows a large initial capacity up to ∼340 mAh/g at a constant current density of 0.2 mA/cm 2 , which is much larger than that of sodium-based homologue. The X-ray diffraction analysis demonstrates that the amorphous character of the nanocrystalline compounds is maintained before and after chemical lithiation reaction. The local crystal structure around manganese in these materials has been determined by performing the combinative micro-Raman and X-ray absorption spectroscopy. From the Mn K-edge X-ray absorption near-edge structure and micro-Raman results, it becomes certain that manganese ions are stabilized in the rhombohedral layered lattice consisting of edge-shared MnO 6 octahedra, and the crystal symmetry is changed into a monoclinic symmetry upon reaction with n-BuLi. The Mn K-edge extended X-ray fine structure analysis reveals that the structural distortion caused by lithiation process is less significant for these nanocrystalline compounds than for the spinel lithium manganate. In this context, the great discharge capacity of the nanocrystalline materials is attributable for the pillaring effect of larger alkali metal ion than lithium ion, providing an expanded interlayer space available for Li insertion. In addition, the I L I -edge X-ray absorption near-edge structure results presented here make it clear that iodine is stabilized as iodate species on the grain boundary or the surface of the nanocrystalline manganese oxyiodide, which helps to maintain the nanocrystalline nature of the present materials before and after Li insertion.

Hydrolysis and condensation of (CH3COCHCOCH3)2SnF(Otert-Am) and (CF3COCHCOCH3)2Sn(Otert-Am)2 gave soluble stannic oxo-oligomers or -polymers including fluorine and β-diketonate groups. Under thermal treatment in air at 550 °C, they yielded nanocrystalline fluorine-doped tin dioxide powders. The amount of remaining ligands in the xerosols depends on the hydrolysis ratio and on the nature of the solvent used, dimethylformamide (DMF) favoring ligand removal. The thermolytic reactions have been investigated by thermogravimetry coupled to mass spectrometry: (1) the β-diketonate ligands pyrolyze in two stages, at 200 and 320 °C, involving two different processes; (2) elimination of polar solvents of high boiling point, such as DMF, occurs up to 300 °C; (3) fluorine is lost as fluorhydric acid from 230 °C. The best strategy to prepare F-doped SnO2 materials by the sol−gel route is thus to start from precursors including Sn−F bonds and to use a polar aprotic solvent of low boiling point such as acetonitrile. It led to nanocrystalline, highly conductive F-doped tin dioxide materials with resistivities 1 order of magnitude lower than that reported for Sb-doped tin dioxide powders.

Chromium-substituted LiMn 1-x Cr x O 2 (0 e x e 0.15) oxides have been prepared by the ion-exchange reaction between R-NaMn 1-x Cr x O 2 and LiBr. From the X-ray diffraction and infrared spectroscopic analyses, all of the present layered compounds are found to be crystallized with monoclinic structure. Additionally, the nitrogen adsorption-desorption isotherm measurements indicate a decrease in crystallite size induced by the replacement of Mn with Cr. According to the electrochemical measurements, the Cr-substituted compounds exhibit better electrochemical performance than the pristine LiMnO 2 . The effects of chromium substitution on the chemical bonding nature of LiMn 1-x Cr x O 2 have been investigated by performing X-ray absorption spectroscopic (XAS) analyses. The Cr K-edge XAS results presented here clarify that the trivalent chromium ions are stabilized in the octahedral site of the (Mn,Cr)O 2 layer before and after the electrochemical charge-discharge process. From the extended X-ray absorption fine structure analyses at the Mn K-edge, it becomes clear that the substitution of manganese with chromium gives rise to a shortening of the Mn-O bonds, leading to the stabilization of Mn in the octahedral site. On the basis of the present experimental findings, we suggest that the superior electrochemical performance of LiMn 1-x Cr x O 2 can be attributed to the enhanced stability of the layered manganese oxide lattice because of the presence of a chromium ion in the octahedral site of the transition metal oxide layer, which hinders the migration of manganese ions into the interlayer lithium sites.