Operando Synchrotron X-ray Diffraction in Calcium Batteries: Insights into the Redox Activity of 1D Ca3CoMO6 (M = Co and Mn).

1D Ca3Co2-z M z O6 (M = Co z = 0, M = Mn z = 1, and M = Fe z = 0.4) were prepared and tested electrochemically. While the iron-containing phase was not found to be active, the iron- and manganese-containing phases were found to be potentially interesting as positive electrode materials for calcium metal-based high-energy battery technologies and were investigated by operando synchrotron X-ray diffraction. Results indicate that electrochemically driven calcium deintercalation from the crystal structure (ca. 0.7 mol per formula unit) takes place upon oxidation in both cases. The oxidized phases have incommensurate modulated crystal structures with the space group R 3m(00γ)0s and a = 9.127(1) Å, c 1 = 2.4226(3) Å and c 2 = 4.1857(3) Å, and γ = 0.579 (M = Co) and a = 9.217(1) Å, c 1 = 4.9076(4) Å and c 2 = 4.3387(4) Å, and γ = 1.139 (M = Mn), which exhibit differences due to the presence of manganese and Mn/Co ordering. The degree of calcium re-intercalation within the structure was found to be extremely limited, if any. Complementary experiments carried out in lithium cells did not show any reversibility either, thus pointing at intrinsic structural/migration constraints in the oxidized phase rather than slow kinetics of high desolvation energies associated with divalent ion charge carriers.

Anisotropic sensor and memory device with a ferromagnetic tunnel barrier as the only magnetic element.

Multiple spin functionalities are probed on Pt/La2Co0.8Mn1.2O6/Nb:SrTiO3, a device composed by a ferromagnetic insulating barrier sandwiched between non-magnetic electrodes. Uniquely, La2Co0.8Mn1.2O6 thin films present strong perpendicular magnetic anisotropy of magnetocrystalline origin, property of major interest for spintronics. The junction has an estimated spin-filtering efficiency of 99.7% and tunneling anisotropic magnetoresistance (TAMR) values up to 30% at low temperatures. This remarkable angular dependence of the magnetoresistance is associated with the magnetic anisotropy whose origin lies in the large spin-orbit interaction of Co2+ which is additionally tuned by the strain of the crystal lattice. Furthermore, we found that the junction can operate as an electrically readable magnetic memory device. The findings of this work demonstrate that a single ferromagnetic insulating barrier with strong magnetocrystalline anisotropy is sufficient for realizing sensor and memory functionalities in a tunneling device based on TAMR.

Hidden Magnetic States Emergent Under Electric Field, In A Room Temperature Composite Magnetoelectric Multiferroic.

The ability to control a magnetic phase with an electric field is of great current interest for a variety of low power electronics in which the magnetic state is used either for information storage or logic operations. Over the past several years, there has been a considerable amount of research on pathways to control the direction of magnetization with an electric field. More recently, an alternative pathway involving the change of the magnetic state (ferromagnet to antiferromagnet) has been proposed. In this paper, we demonstrate electric field control of the Anomalous Hall Transport in a metamagnetic FeRh thin film, accompanying an antiferromagnet (AFM) to ferromagnet (FM) phase transition. This approach provides us with a pathway to "hide" or "reveal" a given ferromagnetic region at zero magnetic field. By converting the AFM phase into the FM phase, the stray field, and hence sensitivity to external fields, is decreased or eliminated. Using detailed structural analyses of FeRh films of varying crystalline quality and chemical order, we relate the direct nanoscale origins of this memory effect to site disorder as well as variations of the net magnetic anisotropy of FM nuclei. Our work opens pathways toward a new generation of antiferromagnetic - ferromagnetic interactions for spintronics.

On the viability of Mg extraction in MgMoN2: a combined experimental and theoretical approach.

Layered MgMoN2 was prepared by solid state reaction at high temperature between Mo and Mg3N2 in N2 which represents a simple synthetic pathway compared to the previously reported method that used NaN3 as the nitrogen source. The crystal structure of MgMoN2 was studied by synchrotron X-ray and neutron powder diffraction. The feasibility of oxidizing this compound and concomitantly extracting magnesium from the structure was assessed by both chemical and electrochemical approaches, using different protocols. The X-ray diffraction patterns of the oxidized samples do not exhibit any relevant difference with respect to that of the as prepared MgMoN2 and no differences in the cell parameters are deduced from Rietveld refinements. No hints pointing at the presence of any amorphous phase are observed either. These results are rationalized through DFT calculated energy barriers for Mg2+ ion migration in MgMoN2.

Isothermal anisotropic magnetoresistance in antiferromagnetic metallic IrMn.

Antiferromagnetic spintronics is an emerging field; antiferromagnets can improve the functionalities of ferromagnets with higher response times, and having the information shielded against external magnetic field. Moreover, a large list of aniferromagnetic semiconductors and metals with Néel temperatures above room temperature exists. In the present manuscript, we persevere in the quest for the limits of how large can anisotropic magnetoresistance be in antiferromagnetic materials with very large spin-orbit coupling. We selected IrMn as a prime example of first-class moment (Mn) and spin-orbit (Ir) combination. Isothermal magnetotransport measurements in an antiferromagnetic-metal(IrMn)/ferromagnetic-insulator thin film bilayer have been performed. The metal/insulator structure with magnetic coupling between both layers allows the measurement of the modulation of the transport properties exclusively in the antiferromagnetic layer. Anisotropic magnetoresistance as large as 0.15% has been found, which is much larger than that for a bare IrMn layer. Interestingly, it has been observed that anisotropic magnetoresistance is strongly influenced by the field cooling conditions, signaling the dependence of the found response on the formation of domains at the magnetic ordering temperature.

Towards a calcium-based rechargeable battery.

The development of a rechargeable battery technology using light electropositive metal anodes would result in a breakthrough in energy density. For multivalent charge carriers (M(n+)), the number of ions that must react to achieve a certain electrochemical capacity is diminished by two (n = 2) or three (n = 3) when compared with Li(+) (ref. ). Whereas proof of concept has been achieved for magnesium, the electrodeposition of calcium has so far been thought to be impossible and research has been restricted to non-rechargeable systems. Here we demonstrate the feasibility of calcium plating at moderate temperatures using conventional organic electrolytes, such as those used for the Li-ion technology. The reversibility of the process on cycling has been ascertained and thus the results presented here constitute the first step towards the development of a new rechargeable battery technology using calcium anodes.

Exploring a novel preparation method of 1D metal organic frameworks based on supercritical CO2.

The preparation of copper(II) one-dimensional MOFs using an eco-efficient method is reported here. This method is based exclusively on using supercritical CO2 as a solvent, without the addition of any other additive or co-solvent. Neutral acetylacetonate copper complexes and two linear linkers, namely, the bidentate 4,4'-bipyridine and 4,4'-trimethylenedipyridine molecules, were reacted under compressed CO2 at 60 °C and 20 MPa for periods of 4 or 24 h. The success achieved in the synthesis of the different studied 1D-MOFs was related to the solubility of the reagents in supercritical CO2. The reaction yield of the synthesized coordination polymers via the supercritical route was close to 100% because both the reactants were almost completely depleted in the performed experiments.

Room-temperature antiferromagnetic memory resistor.

The bistability of ordered spin states in ferromagnets provides the basis for magnetic memory functionality. The latest generation of magnetic random access memories rely on an efficient approach in which magnetic fields are replaced by electrical means for writing and reading the information in ferromagnets. This concept may eventually reduce the sensitivity of ferromagnets to magnetic field perturbations to being a weakness for data retention and the ferromagnetic stray fields to an obstacle for high-density memory integration. Here we report a room-temperature bistable antiferromagnetic (AFM) memory that produces negligible stray fields and is insensitive to strong magnetic fields. We use a resistor made of a FeRh AFM, which orders ferromagnetically roughly 100 K above room temperature, and therefore allows us to set different collective directions for the Fe moments by applied magnetic field. On cooling to room temperature, AFM order sets in with the direction of the AFM moments predetermined by the field and moment direction in the high-temperature ferromagnetic state. For electrical reading, we use an AFM analogue of the anisotropic magnetoresistance. Our microscopic theory modelling confirms that this archetypical spintronic effect, discovered more than 150 years ago in ferromagnets, is also present in AFMs. Our work demonstrates the feasibility of fabricating room-temperature spintronic memories with AFMs, which in turn expands the base of available magnetic materials for devices with properties that cannot be achieved with ferromagnets.

Effect of cation disorder on structural, magnetic and dielectric properties of La2MnCoO6 double perovskite.

The origin of dielectric anomalies and magnetodielectric response of La(2)MnCoO(6) has been investigated by means of ultra-high resolution synchrotron x-ray powder diffraction, neutron powder diffraction, resistivity, magnetization and dielectric measurements. The study has been performed on two different bulk samples presenting different degrees of Mn/Co order: 95 and 74%. Beside the well-known influence on magnetic properties, our results show that the main effect of disorder lies on the electrical resistivity. Bond distances clearly show Mn(4+)/Co(2+) valence states in the well-ordered sample, while for the disordered one this picture still holds. AC resistivity data show dielectric anomalies and a small magnetodielectric effect, but impedance complex plane analyses prove that these phenomena appear at the frequency-temperature region where extrinsic effects dominate the dielectric response.

Magnetic and electronic properties of Bi(0.75)Ca(0.25)MnO(3).

The magnetic, structural and electronic properties of Bi(0.75)Ca(0.25)MnO(3) have been investigated in comparison with those of Bi(0.75)Sr(0.25)MnO(3). Magnetometry, diffraction and muon spin relaxation (µSR) data confirm different structural, magnetic and electronic transitions in the two compounds. The anisotropic changes of cell parameters across the structural transition in Bi(0.75)Ca(0.25)MnO(3) (275 K) differ markedly from the lattice anomalies in Bi(0.75)Sr(0.25)MnO(3) (600 K) and also from those in Bi(0.50)Ca(0.50)MnO(3) (325 K). The ground state of Bi(0.75)Ca(0.25)MnO(3) is characterized by a high degree of spin disorder and frustrated interactions. There is no evidence of a ferromagnetic component in the ground state of Bi(0.75)Ca(0.25)MnO(3). However, the application of a magnetic field (even of a few gauss) produces a continuous progressive polarization of the Mn moments (≈2 µ(B)/Mn at 5 T, ZFC, 5 K). Differences between Ca and Sr perovskites with x = 1/4 are greater than for the x = 1/2 counterparts, and point to distinct ground states and charge/orbital configurations.

Studying avalanches in the ground state of the two-dimensional random-field ising model driven by an external field

We study the exact ground state of the two-dimensional random-field Ising model as a function of both the external applied field B and the standard deviation sigma of the Gaussian random-field distribution. The equilibrium evolution of the magnetization consists in a sequence of discrete jumps. These are very similar to the avalanche behavior found in the out-of-equilibrium version of the same model with local relaxation dynamics. We compare the statistical distributions of magnetization jumps and find that both exhibit power-law behavior for the same value of sigma. The corresponding exponents are compared.