(De)lithiation of spinel ferrites Fe3O4, MgFe2O4, and ZnFe2O4: a combined spectroscopic, diffraction and theory study
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We present an exploration of a family of compositionally complex cubic spinel ferrites featuring combinations of Mg, Fe, Co, Ni, Cu, Mn, and Zn cations, systematically investigating the average and local atomic structures, chemical short-range order, magnetic spin configurations, and magnetic properties. All compositions result in ferrimagnetic average structures with extremely similar local bonding environments; however, the samples display varying degrees of cation inversion and, therefore, differing apparent bulk magnetization. Additionally, first-order reversal curve analysis of the magnetic reversal behavior indicates varying degrees of magnetic ordering and interactions, including potentially local frustration. Finally, reverse Monte Carlo modeling of the spin orientation demonstrates a relationship between the degree of cation inversion and the spin collinearity. Collectively, these observations correlate with differences in synthesis procedures. This work provides a framework for understanding magnetic behavior reported for “high-entropy spinels,” revealing many are likely compositionally complex oxides with differing degrees of chemical short-range order—not meeting the community established criteria for high or medium entropy compounds. Moreover, this work highlights the importance of reporting complete sample processing histories and investigating local to long-range atomic arrangements when evaluating potential entropic mixing effects and assumed property correlations in high entropy materials.
Cobalt and copper ferrite spinels as catalysts in oxidative dehydrogenation of butenes
Spinel lithium ferrite magnetic and crystallographic properties, considering effects of Li and oxygen losses, sintering temperature and cooling rate
How disorder affects magnetic ordering is always an intriguing question, and it becomes even more interesting in the recently rising high entropy oxides due to the extremely high disorder density. However, due to the lack of high-quality single crystal samples, the strong compositional disorder effect on magnetic transition has not been deeply investigated. In this work, we have successfully synthesized high-quality single crystalline high entropy spinel ferrites (Mg 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 ) x Fe 3-x O 4 . Our findings from high-temperature magnetization and neutron diffraction experiments showed ferrimagnetic transitions at 748, 694, and 674 K for x values of 1, 1.5, and 1.8, respectively. Notably, the magnetic transition almost showed no broadening for x values of 1 and 1.5, compared to Fe 3 O 4 . Extended X-ray absorption fine structure measurements provided insights into the elemental distribution among the octahedral and tetrahedral sites. The random distribution of elements across these sites reduced the formation of local clusters and short-range orders, enhancing sample homogeneity and preserving the sharpness of the magnetic transition, despite bond length variation. Here, our study not only marks the first successful synthesis of an HEO bulk single crystal exhibiting long-range magnetic order but also sheds light on the interaction between high configurational entropy and magnetic orderings. This opens new avenues for future research and applications of magnetic high entropy oxides.
We explored a series of highly uniform magnetic nanoparticles (MNPs) with a core-shell nanoarchitecture prepared by an efficient solvothermal approach. In our study, we focused on the water dispersion of MNPs based on two different CoFe 2 O 4 core sizes and the chemical nature of the shell (MnFe 2 O 4 and spinel iron oxide). We performed an uncommon systematic investigation of the time and temperature evolution of the adiabatic heat release at different frequencies of the alternating magnetic field (AMF). Our systematic study elucidates the nontrivial variations in the heating efficiency of core-shell MNPs concerning their structural, magnetic, and morphological properties. In addition, we identified anomalies in the temperature and frequency dependencies of the specific power absorption (SPA). We conclude that after the initial heating phase, the heat release is governed by the competition of the Brown and Néel mechanism. In addition, we demonstrated that a rational parameter sufficiently mirroring the heating ability is the mean magnetic moment per MNP. Our study, thus, paves the road to fine control of the AMF-induced heating by MNPs with fine-tuned structural, chemical, and magnetic parameters. Importantly, we claim that the nontrivial variations of the SPA with the temperature must be considered, e.g., in the emerging concept of MF-assisted catalysis, where the temperature profile influences the undergoing chemical reactions.
Ultra-thin films of low damping ferromagnetic insulators with perpendicular magnetic anisotropy have been identified as critical to advancing spin-based electronics by significantly reducing the threshold for current-induced magnetization switching while enabling new types of hybrid structures or devices. Here, we have developed a new class of ultra-thin spinel structure Li 0.5 Al 1.0 Fe 1.5 O 4 (LAFO) films on MgGa 2 O 4 (MGO) substrates with: 1) perpendicular magnetic anisotropy; 2) low magnetic damping and 3) the absence of degraded or magnetic dead layers. These films have been integrated with epitaxial Pt spin source layers to demonstrate record low magnetization switching currents and high spin-orbit torque efficiencies. These LAFO films on MGO thus combine all of the desirable properties of ferromagnetic insulators with perpendicular magnetic anisotropy, opening new possibilities for spin based electronics.
© 2020 Author(s). We have investigated magnesium aluminum ferrite thin films with a range of iron concentrations and identified the optimal iron content to obtain high crystalline quality thin films with the low magnetic damping required for spin current-based applications. Epitaxial MgAl 2-x FexO4 films with 0.8 < x < 2.0 were grown by pulsed laser deposition on single crystal MgAl2O4 substrates and were characterized structurally and magnetically. We find that the x = 1.5 composition minimizes the room-temperature magnetic damping with a typical Gilbert damping parameter of α eff = 1.8 × 10-3. This minimized damping is governed by a competition between the more robust magnetic ordering with increased iron content, x, and the more defective structure due to larger film-substrate lattice mismatch with increased iron content. The temperature-dependent magnetization curves indicate that Tc is suppressed below room temperature for iron content x ≤ 1.2 and eventually suppressed entirely for x = 0.8. X-ray magnetic circular dichroism results indicate that for all x the magnetic moment is dominated by Fe 3 + cations distributed in a 60:40 ratio on the octahedral and tetrahedral sites, with minimal contribution from Fe 2 + cations. Films with x = 1.4-1.6 exhibit very strong ferromagnetic resonance and low Gilbert damping with α eff = (1.8-6) × 10-3, making them ideal candidates for microwave and spintronic applications.
Effects of lithium and oxygen losses on magnetic and crystallographic properties of spinel lithium ferrite
The use of three-dimensional porous nickel foam as the current collector of the nickel hydroxide electrode adds significantly to the cost of the nickel-based alkaline rechargeable batteries. Although iron is considerably less expensive than nickel, iron corrodes at the operating potential of the nickel hydroxide electrode. We have found that a 70–100 nm thick thermal coating of cobalt ferrite spinel protects the iron from corrosion. Such a coated iron substrate was found to be stable against corrosion even when polarized anodically at 10 mA cm -2 in 30% potassium hydroxide electrolyte for 1000 h. While the thermal coating of cobalt ferrite protected iron against corrosion, incorporation of lithium ions into the coating was found to enhance the electrical conductivity of the coating. XPS and EXAFS studies confirmed that the enhanced conductivity resulted from an increase in the population of Co 3+ in the ferrite spinel lattice. An inexpensive iron (steel) substrate protected by such a coating when used as a nickel hydroxide battery electrode exhibited a specific capacity of 0.25 Ah g -1 at C/5 discharge rate, comparable to a nickel hydroxide electrode based on a relatively expensive nickel foam substrate. The steel-based electrode also exhibited no noticeable degradation over 150 cycles at C/2 rate. This demonstration of a robust and economical steel substrate presents a unique opportunity for reducing the cost of the nickel hydroxide battery electrode in alkaline batteries
The heating abilities of bi-magnetic core–shell nanostructures are studied depending on core size, nature of the shell, and shell thickness.
Soft ferrites are materials of interest for magnetic cores, as used for wireless charging transformers. Their low permeabilities, high resistivity, and magnetic polarization make them interesting for high-power electric vehicle charging and drive systems. The nickel-zinc-doped ferrites are of particular interest; however, the compositional space is quite large with respect to dopant concentrations, stoichiometric ratios and synthesis technique. Nickel-zinc spinel ferrites with varying nickel-zinc ratios prepared by a self-combustion reaction followed by heat treatment exhibit good crystallinity, and their low-temperature Mössbauer spectra show local magnetism and site occupation in agreement with materials prepared by solid-state reaction. Thus, the combustion synthesis method offers a facile tunability of compositions, which, combined with the possibility of rapid characterization of atomic-scale magnetism by Mössbauer spectroscopy, enables advances in the compositional and processing space at a fast pace. Low-temperature Mössbauer spectroscopy data for samples with increasing nickel content reveals a systematic increase in average hyperfine field (2.8 T/Ni) and decrease in average isomer shift (−0.036 mm/s/Ni) that can determine the nickel/zinc content, even in the absence of applied magnetic field data. Furthermore, a gradual evolution of color is also observed with increasing nickel content, albeit trends in color depend on sintering conditions.
Transition metal complexes capable of photoinduced spin crossover have been greatly investigated because of their potential to enable ultrafast optical control of information processing. Yet, any real application of photoswitchable molecules requires that spin crossover be paired with additional functionality such as long-range magnetic order. Important advances combining these functions are notably reported for a number of bimetallic Prussian Blue analogues; however, to date, PBA-based magnetic photoswitches can only operate below 150 K due to loss of magnetic order. In contrast, cobalt ferrite is a ferrimagnetic semiconductor with a Curie temperature of 790 K and extremely favorable magnetic properties by comparison to state-of-the-art PBAs. The mixed valence electronic structure of cobalt ferrite is reminiscent of cobalt–iron PBA, which is a well-known photoswitch. To investigate the potential for photoswitching in this material, we employ transient XUV spectroscopy to probe charge and spin dynamics with element-specific resolution on the femtosecond time scale. Results show that 400 nm light excites a metal-to-metal charge transfer transition, which drives the crossover of high-spin Co 2+ to low-spin Co 3+ with a time constant of 405 ± 29 fs and an internal quantum efficiency of unity. This result establishes the existence of efficient photoswitching in a new class of robust ferrimagnetic spinel ferrites.
Four different compositionally complex multicomponent M 3 O 4 spinels containing 5–8 distinct metals were prepared by a rapid combustion synthesis method or solvothermal synthesis. High resolution synchrotron X-ray diffraction patterns show that the materials consist primarily of spinel phases with small amounts of rock salt impurities, and, in several samples, a minor amount of contracted spinel phase. Materials were investigated as conversion anodes in lithium half-cells and delivered significantly higher capacities than two-component MgFe 2 O 4 made by combustion synthesis. X-ray absorption near-edge structure (XANES) was used to estimate the oxidation states of the metals in the pristine, lithiated (discharged) and delithiated (charged) materials to better understand the redox processes in half cells that led to the improvement. Co, Ni, and Zn are reduced to low oxidation states during lithiation (cell discharge) but are only partially oxidized. The presence of a conductive metallic network that forms after lithiation is thought to account for the improved electrochemical characteristics. Interestingly, in most of the samples, iron is not fully reduced during initial lithiation unlike what happens with a set of related high entropy spinel ferrites studied previously. Finally, the improved electrochemical properties of these materials illustrates both the advantages of complexity and the difficulties in predicting their behavior.
The thermal decomposition approach was used for the synthesis of MFe2O4 magnetic nanoparticles (MNPs) by substituting M as Co, Mn, and Zn. The obtained MNPs were characterized for magneto-structural properties using X-Ray diffraction patterns, FTIR, Raman and Mossbauer spectroscopy techniques which confirm the formation of phase pure cubic spinel ferrite with space group Fd3m and five Raman active modes. The size, morphology, and compositional analysis was performed using HRTEM and EDX where the size of MNPs was found to be less than 10 nm that attains superparamagnetism. The magnetic hyperthermia performance of obtained MNPs was evaluated by induction heating experiments at magnetic field range 13.3 to 26.7 kAm-1. The specific absorption rate (SAR) and intrinsic loss power (ILP) values were determined at different magnetic fields within the human tolerable range and correlated with magneto-structural properties to evaluate its potential for possible magnetic particle hyperthermia therapy.
This work investigates the oxidation of a nickel-based superalloy, namely Alloy X, in water at elevated temperatures: subcritical water at 261°C and 27 MPa, the transition between subcritical and supercritical water at 374°C and 27 MPa, and supercritical water at 380°C and 27 MPa for 100 h. The morphology of the sample surfaces were studied using scanning electron microscopy coupled with focused ion beam milling, and the surface chemistry was investigated using x-ray diffraction, Raman spectroscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy before and after exposure studies. Surfaces of all samples were identified to comprise of a ferrite spinel containing aluminum.
Spin wave-based spintronics are an alternative to conventional electronics due to their potential for efficient energy consumption, improved processing speed, and smaller device dimensions. Low damping magnetic insulators provide the medium for efficient propagation of spin waves for information transfer. Here, we have synthesized by pulsed laser deposition epitaxial spinel structure ferrite thin films of Li 0.5 (Al 1.0 Fe 1.5 )O 4 (LAFO) on (111)-oriented MgAl 2 O 4 that support isotropic magnon propagation in the film plane. Our ferromagnetic resonance measurements show low magnetic damping with a typical Gilbert damping parameter of α = 0.006 and weak-spin–orbit coupling with g = 2.02. These films have low effective magnetization, μ o M eff = 20 mT, similar to that of yttrium iron garnet, the gold standard of low loss magnetic insulators. Our findings show that LAFO is a good candidate as a spin wave medium since it can be grown at low temperatures in different crystal orientations.