Lithiation Mechanism in High-Entropy Oxides as Anode Materials for Li-Ion Batteries: An Operando XAS Study.

High-entropy oxides based on transition metals, such as Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O (TM-HEO), have recently drawn special attention as potential anodes in lithium-ion batteries due to high specific capacity and cycling reversibility. However, the lithiation/delithiation mechanism of such systems is still controversial and not clearly addressed. Here, we report on an operando XAS investigation into TM-HEO-based anodes for lithium-ion cells during the first lithiation/delithiation cycle. This material showed a high specific capacity exceeding 600 mAh g-1 at 0.1 C and Coulombic efficiency very close to unity. The combination of functional and advanced spectroscopic studies revealed complex charging mechanisms, developing through the reduction of transition-metal (TM) cations, which triggers the conversion reaction below 1.0 V. The conversion is irreversible and incomplete, leading to the final collapse of the HEO rock-salt structure. Other redox processes are therefore discussed and called to account for the observed cycling behavior of the TM-HEO-based anode. Despite the irreversible phenomena, the HEO cubic structure remains intact for ∼60% of lithiation capacity, so proving the beneficial role of the configuration entropy in enhancing the stability of the HEO rock-salt structure during the redox phenomena.

CdEr2Se4: a new erbium spin ice system in a spinel structure.

Here we present a detailed study of the spinel CdEr2Se4 and show it to be a new instance of spin ice, the first one in an erbium material and the first one in a spinel. Definitive experimental evidence comes from the temperature dependence of the magnetic entropy, which shows an excellent agreement with the predicted behavior for a spin ice state. Crystal field calculations demonstrate that the change in the local environment from that of the titanates completely alters the rare-earth anisotropy giving rise, in the case of Er3+, to the required Ising anisotropy, when Er2Ti2O7 behaves as an XY antiferromagnet. This finding opens up the possibility of new exotic ground states within the CdR2Se4 and CdR2Se4 families.

Optical evidence for symmetry changes above the Néel temperature of KCuF3.

We report on optical measurements of the 1D Heisenberg antiferromagnet KCuF3. The crystal-field excitations of the Cu2+ ions have been observed and their temperature dependence can be understood in terms of magnetic and exchange-induced dipole mechanisms and vibronic interactions. Above TN we observe a new temperature scale TS characterized by the emergence of narrow absorption features that correlate with changes of the orbital ordering as observed by Paolasini et al. [Phys. Rev. Lett. 88, 106403 (2002)]. The appearance of these optical transitions provides evidence for a symmetry change above the Néel temperature that affects the orbital ordering and paves the way for the antiferromagnetic ordering.

Dynamical Dzyaloshinsky-Moriya interaction in KCuF3.

The spin dynamics of the prototypical quasi-one-dimensional antiferromagnetic Heisenberg spin S=1/2 chain KCuF3 is investigated by electron spin resonance spectroscopy. Our analysis shows that the peculiarities of the spin dynamics require a new dynamical form of the antisymmetric anisotropic spin-spin interaction. This dynamical Dzyaloshinsky-Moriya interaction is related to strong oscillations of the bridging fluorine ions perpendicular to the crystallographic c axis. This new mechanism allows us to resolve consistently the controversies in observation of the magnetic and structural properties of this orbitally ordered perovskite compound.

Strong electronic correlations in LixZnPc organic metals.

Nuclear magnetic resonance, electron paramagnetic resonance and magnetization measurements show that bulk LixZnPc are strongly correlated one-dimensional metals. The temperature dependence of the nuclear spin-lattice relaxation rate 1/T_{1} and of the static uniform susceptibility chi_{S} on approaching room temperature are characteristic of a Fermi liquid. Moreover, while for x approximately 2 the electrons are delocalized down to low temperature, for x-->4 a tendency towards localization is noticed upon cooling, yielding an increase both in 1/T_{1} and chi_{s}. The x dependence of the effective density of states at the Fermi level D(E_{F}) displays a sharp enhancement for x approximately 2, at the half filling of the ZnPc lowest unoccupied molecular orbitals. This suggests that LixZnPc is on the edge of a metal-insulator transition where enhanced superconducting fluctuations could develop.

Anomalous dispersion of longitudinal optical phonons in Nd(1.86)Ce(0.14)CuO(4+delta) determined by inelastic x-ray scattering.

The phonon dispersions of Nd(1.86)Ce(0.14)CuO(4+delta) along the [xi,0,0] direction have been determined by inelastic x-ray scattering. Compared to the undoped parent compound, the two highest longitudinal phonon branches, associated with the Cu-O bond stretching and out-of-plane oxygen vibration, are shifted to lower energies. Moreover, an anomalous softening of the bond-stretching band is observed at about q = (0.2,0,0). These signatures provide evidence for strong electron-phonon coupling in this electron-doped high-temperature superconductor.

Coupling between spin and orbital degrees of freedom in KCuF3.

We present the results of resonant x-ray scattering experiments on KCuF3. Structurally forbidden reflections, corresponding to magnetic and 3d-orbital long-range order, have been observed. Integrated intensities have been measured as a function of incident energy, polarization, azimuthal angle, and temperature. The results give evidence for a strong coupling between orbital and spin degrees of freedom. The interplay between magnetic and orbital order parameters is revealed by the temperature dependence of the intensity of orbital Bragg peaks.