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In this work, we report the presence of surface-densified phases (β-Ni5O8, γ-Ni3O4, and δ-Ni7O8) in LiNiO2 (LNO)- and LiNi0.8Al0.2O2 (LNA)-layered compounds by combined atomic level scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). These surface phases form upon electrochemical aging at high state of charge corresponding to a fully delithiated state. A unique feature of these phases is the periodic occupancy by Ni2+ in the Li layer. This periodic Ni occupancy gives rise to extra diffraction reflections, which are qualitatively similar to those of the LiNi2O4 spinel structure, but these surface phases have a lower Ni valence state and cation content than spinel. These experimental results confirm the presence of thermodynamically stable surface phases and provide new insights into the phenomena of surface phase formation in Ni-rich layered structures.

This paper reports new insights into structural and chemical evolution of surface phases of LiNi0.8Co0.15Al0.05O2 (NCA) held at constant high voltages (up to 4.75 V) as well as high temperatures (6...

Practical utilization of energy densities near the theoretical limit for R3m layered oxide positive electrode materials is dependent on the stability of the electrochemical performance of these materials at or near full delithiation. To develop new chemistries and novel approaches toward the improvement of the electrochemical performance of these materials at such high states of charge, a robust understanding of the failure mechanisms limiting current materials is necessary. Thorough analysis of LixCo1–yAlyO2 and LixNi1–yAlyO2 as well as LixNi0.8Co0.2O2 and LixNi0.8Co0.15Al0.05O2 (1 ≥ x ≥ 0 and 0.2 ≥ y ≥ 0) enabled the identification of key relationships between the transition metal chemistry of the electrode, its structural stability, and cycling characteristics at or near complete delithiation (4.75 V). Extensive characterization of these materials was achieved by a multitude of physical and electrochemical techniques to investigate the relative importance of surface vs bulk phenomena. The resulting in...

We report the formation of complex core–shell and three-layer Mn–Bi nanoparticles in a single step inert-gas condensation process. These structures have been achieved by controlling the thermal environment of the nanoparticles. High resolution transmission electron microscopy, high-angle annular dark-field imaging in scanning transmission electron microscopy mode, and elemental mapping by energy dispersive spectroscopy have been used to determine the crystal structure and chemical composition of the nanoparticles. These particles exist in two forms: (1) a crystalline Bi core with an amorphous Mn-rich shell, and (2) a crystalline Bi annular shell between two amorphous layers with high Mn concentration. These particles show significant magnetic hysteresis possibly arising from the change in bond length between Mn atoms introduced by Bi atoms in the bonding environment of the Mn atoms.

Bulk magnetic materials with the noncentrosymmetric cubic B20 structure are fascinating due to skyrmion spin structures associated with Dzyaloshinskii–Moriya interactions, but the size of skyrmions are generally larger than 50 nm. The control of such spin structures in the 10 nm size ranges is essential to explore them for spintronics, ultra-high-density magnetic recording, and other applications. In this study, we have fabricated MnSi nanoparticles with average sizes of 9.7, 13.1 and 17.7 nm and investigated their structural and magnetic properties. X-ray diffraction and transmission electron microscope studies show that the MnSi nanoparticles crystallize in the cubic B20 structure. Field-dependent dc susceptibility data of the MnSi samples with average particle sizes of 17.7 and 13.1 nm show anomalies in limited field (about 25–400 Oe) and temperature (25 K–43 K) ranges. These features are similar to the signature of the skyrmion-like spin structures observed below the Curie temperature of MnSi. Our results also show that this anomalous behavior is size-dependent and suppressed in the smallest nanoparticles (9.7 nm), and this suppression is interpreted as a confinement effect that leads to a truncation of the skyrmion structure.

Amorphous Fe32Ni52Zr3B13, prepared by rapid solidification, undergoes crystallization during high-energy mechanical milling. The resulting structure consists of face-centered cubic (fcc) FeNi and Zr3Ni20B6 nanocrystallites. Structural evolution and defect analysis of as-solidified Fe32Ni52Zr3B13 ribbons with different milling times is investigated. From the differential thermal analysis (DTA) curve of amorphous ribbons, exothermic peaks were observed at 415 °C and 475 °C corresponding to the crystallization of fcc Zr3Ni20B6 phase and fcc FeNi phase, respectively. However, high-energy mechanical milling induces the formation of FeNi within the first 2 h of mechanical milling. Further milling induces the crystallization of Zr3Ni20B6. Doppler broadening positron annihilation spectroscopy (DBPAS) was used to investigate vacancy-type defects. The milling-induced crystallization appears to be related to enhanced vacancy-type defect concentrations allowing growth of pre-existing Fe(Ni) nuclei. The milling and enhanced vacancy concentration also de-stabilizes the glass, leading to decreased crystallization temperatures for both phases, and ultimately eliminating the glass transition altogether.

Mn-based silicides are fascinating due to their exotic spin textures and unique crystal structures, but the low magnetic ordering temperatures and/or small magnetic moments of bulk alloys are major impediments to their use in practical applications. In sharp contrast to bulk Mn5Si3, which is paramagnetic at room temperature and exhibits low-temperature antiferromagnetic ordering, we show ferromagnetic ordering in Mn5Si3 nanoparticles with a high Curie temperature (Tc ≈ 590 K). The Mn5Si3 nanoparticles have an average size of 8.6 nm and also exhibit large saturation magnetic polarizations (Js = 10.1 kG at 300 K and 12.4 kG at 3 K) and appreciable magnetocrystalline anisotropy constants (K1 = 6.2 Mergs/cm(3) at 300 K and at 12.8 Mergs/cm(3) at 3 K). The drastic change of the magnetic ordering and properties in the nanoparticles are attributed to low-dimensional and quantum-confinement effects, evident from first-principle density-functional-theory calculations.

High-anisotropy arc-melted and field-annealed Mn100−x Bi x (x = 50–65) alloys have been investigated. Samples predominantly consist of low-temperature phase (LTP) MnBi and elemental Bi, where the LTP volume fraction and sample magnetization decrease with increasing x. All samples are hard ferromagnetic at room temperature and demonstrate a structural and magnetic phase transition at 630 K. For Mn35Bi65, the highest values for coercivity (4.6 kOe), magnetization remanence ratio (0.97), and energy product (4.9 MGOe) are measured at 540 K, near the melting point of bismuth. We explain the trend in magnetic properties as a consequence of c-axis alignment of MnBi grains facilitated by the molten Bi during magnetic field annealing.

The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1 V (versus Li/Li+) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li1–xNi0.8Co0.15Al0.05O2 binder-free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and 4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of sign...

We report the fabrication of a rare-earth-free permanent-magnet material Co3Si in the form of nanoparticles and investigate its magnetic properties by experiments and density-functional theory (DFT). The DFT calculations show that bulk Co3Si has an easy-plane anisotropy with a high K1 ≈ −64 Merg/cm3 (−6.4 MJ/m3) and magnetic polarization of 9.2 kG (0.92 T). In spite of having a negative anisotropy that generally leads to negligibly low coercivities in bulk crystals, Co3Si nanoparticles exhibit high coercivities (17.4 kOe at 10 K and 4.3 kOe at 300 K). This result is a consequence of the unique nanostructure made possible by an effective easy-axis alignment in the cluster-deposition method and explained using micromagnetic analysis as a nanoscale phenomenon involving quantum-mechanical exchange interactions.