Low-Temperature Charging and Aging Mechanisms of Si/C Composite Anodes in Li-Ion Batteries: An Operando Neutron Scattering Study.

The addition of Si compounds to graphite anodes has become an attractive way of increasing the practical specific energies in Li-ion cells. Previous studies involving Si/C anodes lacked direct insight into the processes occurring in full cells during low-temperature operation. In this study, a powerful combination of operando neutron diffraction, electrochemical tests, and post-mortem analysis is used for the investigation of Li-ion cells. 18650-type cylindrical cells in two different aging states are investigated by operando neutron diffraction. The experiments reveal deep insights and important trends in low-temperature charging mechanisms involving intercalation, alloying, Li metal deposition, and relaxation processes as a function of charging C-rates and temperatures. Additionally, the main aging mechanism caused by long-term cycling and interesting synergistic effects of Si and graphite are elucidated.

Suppression of inherent ferromagnetism in Pr-doped CeO2 nanocrystals.

Ce(1-x)Pr(x)O(2-δ) (0 ≤ x ≤ 0.4) nanocrystals were synthesized by self-propagating method and thoroughly characterized using X-ray diffraction, Raman and X-ray photoelectron spectroscopy and magnetic measurements. Undoped CeO2 nanocrystals exhibited intrinsic ferromagnetism at room temperature. Despite the increased concentration of oxygen vacancies in doped samples, our results showed that ferromagnetic ordering rapidly degrades with Pr doping. The suppression of ferromagnetism can be explained in terms of the different dopant valence state, the different nature of the vacancies formed in Pr-doped samples and their ability/disability to establish the ferromagnetic ordering.

Potential-induced conformational changes in an alpha-CN-terthiophene thiolate film on GaAs(110).

Second harmonic generation (SHG) investigations on alpha-CN-terthiophene-thiolate-covered GaAs(110) electrodes in 1 N H2SO4 solution revealed significant changes in the rotational anisotropy of the SH response. The enhancement of the 1- and the 3-fold contributions around -250 mV suggests changes in the symmetry properties of the delocalized electron system due to an alteration of the adsorption geometry induced by the applied potentials. The analysis of the EIS data showed that in the potential region where the SH signal exhibits the more important changes the Mott-Schottky plot undergoes a pronounced shift to more negative potentials as a result of the charging of the surface states grouped about 1.06 eV below the conduction band edge. Semiempirical MO calculations suggest that the most energetically favorable interaction implies electron transfer from the semiconductor conduction band to the lowest unoccupied molecular orbital of the organic molecule with epsilon(LUMO)=-1.707 eV. Such a chemisorption bond bringing the organic molecule to a quasi-planar position is well supported by the major changes in the XPS spectra of the electrochemically biased samples with respect to the as-prepared ones. Two distinct N 1s species instead of one and a shift of 1.6 eV to higher BE of the terthiophene S 2s core level are strong evidence for a potential-induced change in the adsorption geometry. Taking into account that the acceptor-like surface state group located close to the semiconductor valence edge (EC,S=-1.06 eV) may correspond to the LUMO level (shifted downward by the adsorption process), we assume that the organic molecule, initially adsorbed by the thiolate end, undergoes a conformational change from a tilted to an almost flat position when the applied potential brings the semiconductor Fermi level into its neighborhood. This assumption is in a very good agreement with the potential-induced variation in the thiol thickness estimated from the thiol capacitance.

Surface states- and field-effects at p- and n-doped GaAs(111)A/solution interface.

We have investigated the behaviour of n- and p-doped GaAs(111)A electrodes in sulfuric acid solution by electrochemical impedance spectroscopy (EIS) and second harmonic generation (SHG) measurements. The potential dependence of the SHG response was found to be closely related to the changes in the surface state population, as revealed by analysis of the impedance data. The nature of the majority of carriers turned out to be a key factor in shaping the surface state- and field-effect on the second harmonic generation process.