RESUMO
Thermal treatment of the Tavorite-type material FePO(4)·H(2)O leads to the formation of two crystallized iron phosphates, very similar in structure. Their structural description is proposed taking into account results obtained from complementary characterization tools (thermal analyses, diffraction, and spectroscopy). These structures are similar to that of the pristine material FePO(4)·H(2)O: iron atoms are distributed between the chains of corner-sharing FeO(6) octahedra observed in FePO(4)·H(2)O and the octahedra from the tunnels previously empty, in good agreement with the formation of a Fe(4/3)PO(4)(OH)-type phase. The formation of an extra disordered phase was also proposed. These samples obtained by thermal-treatment of FePO(4)·H(2)O also intercalate lithium ions through the reduction of Fe(3+) to Fe(2+) at an average voltage of ~2.6 V (vs Li(+)/Li), with a good cyclability and a reversible capacity around 120 mA h g(-1) (>160 mA h g(-1) during the first discharge).
RESUMO
A dual redox process involving Ti3+/Ti4+ cation species and S2-/(S2)2- anion species is highlighted in oxygenated lithium titanium sulfide thin film electrodes during lithium (de)insertion, leading to a high specific capacity. These cathodes for all-solid-state lithium-ion microbatteries are synthesized by sputtering of LiTiS2 targets prepared by different means. The limited oxygenation of the films that is induced during the sputtering process favors the occurrence of the S2-/(S2)2- redox process at the expense of the Ti3+/Ti4+ one during the battery operation, and influences its voltage profile. Finally, a perfect reversibility of both electrochemical processes is observed, whatever the initial film composition. All-solid-state lithium microbatteries using these amorphous lithiated titanium disulfide thin films and operated between 1.5 and 3.0 V/Li+/Li deliver a greater capacity (210-270 mAh g-1) than LiCoO2, with a perfect capacity retention (-0.0015% cycle-1).
RESUMO
CuO thin films were prepared by radio frequency magnetron sputtering using a copper target in a (Ar + O2) reactive mixture. Different sputtering parameters were varied including oxygen flow rate, total pressure, target-substrate distance, substrate temperature and target orientation. As expected, the thin film chemical composition is strongly dependent on the oxygen flow rate. CuO thin films having a good electronic conductivity (9.3 × 10(-1) S·cm(-1)) were obtained with an oxygen concentration of 12%. The texture and the columnar growth are amplified when the target is tilted. Preliminary electrochemical results highlight that CuO thin film performances in lithium systems are tightly related to their morphology and structure.
RESUMO
Pure tavorite LiFePO4(OH) was synthesized through a hydrothermal route. A fine structural analysis was done by X-ray and neutron diffraction techniques. The structure consists of a three-dimensional network with iron(III) octahedra (FeO6) sharing corners, forming chains that run along the b direction. These chains are interconnected by PO4 tetrahedra, such as the resulting framework encloses tunnels of two different sizes running along the a and c axis. The lithium and hydrogen atoms were precisely localized in these tunnels. Theoretical (GGA + U) calculations performed for LiFePO4X materials (X = OH, F) confirmed our results and revealed that a unique lithium position is expected in LiFePO4(OH), as experimentally observed. For the first time, lithium intercalation was shown to occur in LiFePO4(OH) through the reduction of Fe3+ to Fe2+ at an average voltage of ~2.3 V (vs. Li(+)/Li) with a good cyclability.