Search

Abstract: Li2Ti6O13 has been prepared from Na2Ti6O13 by Li ion exchange in molten LiNO3 at 325°C. Chemical analysis and powder X-ray diffraction study of the reaction product respectively indicate that total Na/Li exchange takes place and the Ti–O framework of the Na2Ti6O13 parent structure is kept under those experimental conditions. Therefore, Li2Ti6O13 has been obtained with the mentioned parent structure. An important change is that particle size is decreased significantly which is favoring lithium insertion. Electrochemical study shows that Li2Ti6O13 inserts ca. 5 Li per formula unit in the voltage range 1.5–1.0V vs. Li+/Li, yielding a specific discharge capacity of 250mAhg−1 under equilibrium conditions. Insertion occurs at an average equilibrium voltage of 1.5V which is observed for oxides and titanates where Ti(IV)/Ti(III) is the active redox couple. However, a capacity loss of ca. 30% is observed due to a phase transformation occurring during the first discharge. After the first redox cycle a high reversible capacity is obtained (ca. 160mAhg−1 at C/12) and retained upon cycling. Taking into consideration these results, we propose Li2Ti6O13 as an interesting material to be further investigated as the anode of lithium ion batteries. [ABSTRACT FROM AUTHOR]

Abstract: The α-polymorph of Li3FeF6 has been obtained at room temperature by a precipitation reaction from aqueous solution. This easy procedure that does not require any further annealing at high temperature yields a white powder with particles sizes ranging from 250 to 400nm. After proper processing by mechanical milling, particle sizes clearly below 100nm are achieved and this fluoride reacts reversibly with lithium at an average voltage of 3.1V, which is expected for the Fe3+/Fe2+ redox couple. After 12h of ball milling observed average particle size is ca. 50nm and a reversible capacity of 100mAhg−1 is obtained. This corresponds to 70% of the theoretical capacity expected for the one electron reduction of Fe3+. The mentioned capacity is fairly kept upon cycling making the new material useful as the positive electrode in lithium batteries. This is the very first time that a material for cathode application in lithium batteries is prepared at room temperature and from aqueous solution, a procedure which is easily scalable and hence of high industrial interest. [Copyright &y& Elsevier]

Abstract: We describe the synthesis, crystal structure, magnetic and electrochemical characterization of new rock salt-related oxides of formula, Li3 M 2RuO6 (M=Co, Ni). The M=Co oxide adopts the LiCoO2 (R-3m) structure, where sheets of LiO6 and (Co2/Ru)O6 octahedra are alternately stacked along the c-direction. The M=Ni oxide also adopts a similar layered structure related to Li2TiO3, where partial mixing of Li and Ni/Ru atoms lowers the symmetry to monoclinic (C2/c). Magnetic susceptibility measurements reveal that in Li3Co2RuO6, the oxidation states of transition metal ions are Co3+ (S=0), Co2+ (S=1/2) and Ru4+ (S=1), all of them in low-spin configuration and at 10K, the material orders antiferromagnetically. Analogous Li3Ni2RuO6 presents a ferrimagnetic behavior with a Curie temperature of 100K. The differences in the magnetic behavior have been explained in terms of differences in the crystal structure. Electrochemical studies correlate well with both magnetic properties and crystal structure. Li-transition metal intermixing may be at the origin of the more impeded oxidation of Li3Ni2RuO6 when compared to Li3Co2RuO6. Interestingly high first charge capacities (between ca. 160 and 180mAhg−1) corresponding to ca. 2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory enough to consider these materials as alternatives to LiCoO2. [Copyright &y& Elsevier]