Prussian Blue Analogues as Positive Electrodes for Mg Batteries: Insights into Mg2+ Intercalation.

Potassium manganese hexacianoferrate has been prepared by co-precipitation from manganese (II) chloride and potassium citrate, with chemical analysis yielding the formula K1.72 Mn[Fe(CN)6 ]0.92 □0.08 ⋅ 1.1H2 O (KMnHCF). Its X-ray diffraction pattern is consistent with a monoclinic structure (space group P 21 /n, no. 14) with cell parameters a=10.1202(6)Å, b=7.2890(5)Å, c=7.0193(4)Å, and ß=89.90(1)°. Its redox behavior has been studied in magnesium containing electrolytes. Both K+ ions deintercalated from the structure upon oxidation and contamination with Na+ ions coming from the separator were found to interfere in the electrochemical response. In the absence of alkaline ions, pre-oxidized manganese hexacianoferrate showed reversible magnesium intercalation, and the process has been studied by operando synchrotron X-ray diffraction. The location of Mg2+ ions in the crystal structure was not possible with the available experimental data. Still, density functional theory simulations indicated that the most favorable position for Mg2+ intercalation is at 32f sites (considering a pseudo cubic F m-3m phase), which are located between 8c and Mn sites.

High-Temperature Synthesis of Ferromagnetic Eu3Ta3(O,N)9 with a Triple Perovskite Structure.

Europium tantalum perovskite oxynitrides were prepared by a new high-temperature solid-state synthesis under N2 or N2/H2 gas. The nitrogen stoichiometry was tuned from 0.63 to 1.78 atoms per Eu or Ta atom, starting with appropriate N/O ratios in the mixture of the reactants Eu2O3, EuN and Ta3N5, or Eu2O3 and TaON, which was treated at 1200 °C for 3 h. Two phases were isolated with compositions EuTaO2.37N0.63 and Eu3Ta3O3.66N5.34, showing different crystal structures and magnetic properties. Electron diffraction and Rietveld refinement of synchrotron radiation X-ray diffraction indicated that EuTaO2.37N0.63 is a simple perovskite with cubic Pm3̅m structure and cell parameter a = 4.02043(1) Å, whereas the new compound Eu3Ta3O3.66N5.34 is the first example of a triple perovskite oxynitride and shows space group P4/mmm with crystal parameters a = 3.99610(2), c = 11.96238(9) Å. The tripling of the c-axis in this phase is a consequence of the partial ordering of europium atoms with different charges in two A sites of the perovskite structure with relative ratio 2:1, where the formal oxidation states +3 and +2 are respectively dominant. Magnetic data provide evidence of ferromagnetic ordering developing at low temperatures in both oxynitrides, with saturation magnetization of about 6 µB and 3 µB per Eu ion for EuTaO2.37N0.63 and the triple perovskite Eu3Ta3O3.66N5.34 respectively, and corresponding Curie temperatures of about 7 and 3 K, which is in agreement with the lower proportion of Eu2+ in the latter compound.

Spin-to-Charge Conversion in All-Oxide La2/3Sr1/3MnO3/SrIrO3 Heterostructures.

Spin injection and spin-charge conversion processes in all-oxide La2/3Sr1/3MnO3/SrIrO3 (LSMO/SIO) heterostructures with different SIO layer thickness and interfacial features have been studied. Ferromagnetic resonance (FMR) technique has been used to generate pure spin currents by spin pumping (SP) in ferromagnetic (FM) half-metallic LSMO. The change of the resonance linewidth in bare LSMO layers and LSMO/SIO heterostructures suggests a successful spin injection into the SIO layers. However, low values of the spin mixing conductance, compared to more traditional permalloy (Py)/Pt or yttrium iron garnet (YIG)/Pt systems, are found. A thorough analysis of the interfaces by high-resolution scanning transmission electron microscopy (HR-STEM) imaging suggests that they are structurally clean and atomic sharp, but a compositional analysis by energy-dispersive X-ray spectroscopy (EDS) reveals the interdiffusion of La, Ir, and Mn atomic species in the first atomic layers close to the interface. Inverse spin Hall effect (ISHE) measurements evidence that interfacial features play a very relevant role in controlling the effectiveness of the spin injection process and low transversal ISHE voltage signals are detected. In addition, it is found that larger voltage signals are detected for the lowest SIO layer thickness highlighting the role of the spin diffusion length (λsd)/SIO layer thickness ratio. The values of ISHE voltage are rather low but allow us to determine the spin Hall angle of SIO (θSH ≈ 1.12% at T = 250 K), which is remarkably similar to that obtained for the well-known Py/Pt system, therefore suggesting that SIO could be a promising spin-Hall material.

Synchrotron radiation based operando characterization of battery materials.

Synchrotron radiation based techniques are powerful tools for battery research and allow probing a wide range of length scales, with different depth sensitivities and spatial/temporal resolutions. Operando experiments enable characterization during functioning of the cell and are thus a precious tool to elucidate the reaction mechanisms taking place. In this perspective, the current state of the art for the most relevant techniques (scattering, spectroscopy, and imaging) is discussed together with the bottlenecks to address, either specific for application in the battery field or more generic. The former includes the improvement of cell designs, multi-modal characterization and development of protocols for automated or at least semi-automated data analysis to quickly process the huge amount of data resulting from operando experiments. Given the recent evolution in these areas, accelerated progress is expected in the years to come, which should in turn foster battery performance improvements.

Artificial Graphene Spin Polarized Electrode for Magnetic Tunnel Junctions.

2D materials offer the ability to expose their electronic structure to manipulations by a proximity effect. This could be harnessed to craft properties of 2D interfaces and van der Waals heterostructures in devices and quantum materials. We explore the possibility to create an artificial spin polarized electrode from graphene through proximity interaction with a ferromagnetic insulator to be used in a magnetic tunnel junction (MTJ). Ferromagnetic insulator/graphene artificial electrodes were fabricated and integrated in MTJs based on spin analyzers. Evidence of the emergence of spin polarization in proximitized graphene layers was observed through the occurrence of tunnel magnetoresistance. We deduced a spin dependent splitting of graphene's Dirac band structure (∼15 meV) induced by the proximity effect, potentially leading to full spin polarization and opening the way to gating. The extracted spin signals illustrate the potential of 2D quantum materials based on proximity effects to craft spintronics functionalities, from vertical MTJs memory cells to logic circuits.

X-ray Absorption Spectroscopy Study of Thickness Effects on the Structural and Magnetic Properties of Pr2-δNi1-xMn1+xO6-y Double Perovskite Thin Films.

In this work, we report a systematic study of the influence of film thickness on the structural and magnetic properties of epitaxial thin films of Pr2-δNi1-xMn1+xO6-y (PNMO) double perovskite grown on top of two different (001)-SrTiO3 and (001)-LaAlO3 substrates by RF magnetron sputtering. A strong dependence of the structural and magnetic properties on the film thickness is found. The ferromagnetic transition temperature (TC) and saturation magnetization (Ms) are found to decrease when reducing the film thickness. In our case, the thinnest films show a loss of ferromagnetism at the film-substrate interface. In addition, the electronic structure of some characteristic PNMO samples is deeply analyzed using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) measurements and compared with theoretical simulations. Our results show that the oxidation states of Ni and Mn ions are stabilized as Ni2+ and Mn4+, thus the ferromagnetism is mainly due to Ni2+-O-Mn4+ superexchange interactions, even in samples with poor ferromagnetic properties. XMCD results also make evident large variations on the spin and orbital contributions to the magnetic moment as the film's thickness decreases.

ß-V2O5 as Magnesium Intercalation Cathode.

Magnesium batteries have attracted great attention as an alternative to Li-ion batteries but still suffer from limited choice of positive electrode materials. V2O5 exhibits high theoretical capacities, but previous studies have been mostly limited to α-V2O5. Herein, we report on the ß-V2O5 polymorph as a Mg intercalation electrode. The structural changes associated with the Mg2+ (de-) intercalation were analyzed by a combination of several characterization techniques: in situ high resolution X-ray diffraction, scanning transmission electron microscopy, electron energy-loss spectroscopy, and X-ray absorption spectroscopy. The reversible capacity reached 361 mAh g-1, the highest value found at room temperature for V2O5 polymorphs.

Optimization of the Growth Process of Double Perovskite Pr2-δNi1-xMn1+xO6-y Epitaxial Thin Films by RF Sputtering.

Epitaxial thin films of Pr2-δNi1-xMn1+xO6-y (PNMO) double perovskite were grown on (001)-oriented SrTiO3 substrates by RF magnetron sputtering. The influence of the growth parameters (oxygen pressure, substrate temperature, and annealing treatments) on the structural, magnetic and transport properties, and stoichiometry of the films was thoroughly investigated. It is found that high-quality epitaxial, insulating, and ferromagnetic PNMO thin films can only be obtained in a narrow deposition parameter window. It is shown that a careful selection of the growth conditions allows for obtaining a high degree of Ni/Mn cation ordering, which is reflected in the values of the Curie temperature, TC, and saturation magnetization, MS, which are very close to those of bulk material.

Suppression of spin rectification effects in spin pumping experiments.

Spin pumping (SP) is a well-established method to generate pure spin currents allowing efficient spin injection into metals and semiconductors avoiding the problem of impedance mismatch. However, to disentangle pure spin currents from parasitic effects due to spin rectification effects (SRE) is a difficult task that is seriously hampering further developments. Here we propose a simple method that allows suppressing SRE contribution to inverse spin Hall effect (ISHE) voltage signal avoiding long and tedious angle-dependent measurements. We show an experimental study in the well-known Py/Pt system by using a coplanar waveguide (CPW). Results obtained demonstrate that the sign and size of the measured transverse voltage signal depends on the width of the sample along the CPW active line. A progressive reduction of this width evidences that SRE contribution to the measured transverse voltage signal becomes negligibly small for sample width below 200 µm. A numerical solution of the Maxwell equations in the CPW-sample setup, by using the Landau-Lifshitz equation with the Gilbert damping term (LLG) as the constitutive equation of the media, and with the proper set of boundary conditions, confirms the obtained experimental results.

High-Temperature Synthesis and Dielectric Properties of LaTaON2.

The development of new synthetic methodologies of perovskite oxynitrides is challenging but necessary for the search of new compounds and the investigation of new properties. Here, we report a new method of preparation of the perovskite LaTaON2 that has been investigated as a pigment and photocatalyst for water splitting. The synthesis proceeds through the solid-state reactions under N2 at 1500 °C between La2O3, LaN, and Ta3N5 or between LaN and TaON, which are completed after 3 h and lead to sintered, highly crystalline samples with particle sizes up to 1 µm. Nitrogen-deficient samples LaTaO1+xN2-x with x ≤ 0.35 are prepared by changing the N/O ratio in the mixture of reactants. Electron diffraction, synchrotron diffraction, and neutron diffraction studies on stoichiometric and nitrogen-deficient compounds indicate that they crystallize in the monoclinic space group I2/m with lattice parameters for LaTaON2 of a = 5.71458(7), b = 8.05987(10), c = 5.74772(6) Å, and ß = 89.982(3)°. The three anion sites of the I2/m structure are partially occupied by oxygen and nitrogen, with a preference of nitride for two positions with occupancies of 77 and 88%. This anion distribution is different from that reported in previous studies of samples prepared by ammonolysis at lower temperature, suggesting that the synthesis conditions affect the anion order of this perovskite. Optical measurements indicate a band gap of about 1.9 eV, which is close to that observed in samples prepared by other methods. The determined dielectric permittivity for LaTaON2 εr ≈ 200, reported for the first time for a highly nitrided pseudocubic perovskite, is similar to that observed in perovskites with one nitrogen per formula.

Formation of Nickel Oxide Nanocuboids in Ferromagnetic La2Ni1-xMn1+xO6.

The control of the spontaneous formation of nanostructures at the surface of thin films is of strong interest in many different fields, from catalysts to microelectronics, because surface and interfacial properties may be substantially enhanced. Here, we analyze the formation of nickel oxide nanocuboids on top of La2Ni1-xMn1+xO6 double perovskite ferromagnetic thin films, epitaxially grown on SrTiO3 (001) substrates by radio-frequency (RF) magnetron sputtering. We show that, by annealing the films at high temperature under high oxygen partial pressure, the spontaneous segregation of nanocuboids is enhanced. The evolution of the structural and magnetic properties of the films is studied as a function of the annealing treatments at different temperatures. It is shown that the formation of NiOx nanocuboids leads to a nanostructured film surface with regions of locally different electrical transport characteristics.

Rapid Thermal Annealing of Double Perovskite Thin Films Formed by Polymer Assisted Deposition.

The annealing process is an important step common to epitaxial films prepared by chemical solution deposition methods. It is so because the final microstructure of the films can be severely affected by the precise features of the thermal processing. In this work we analyze the structural and magnetic properties of double perovskite La2CoMnO6 and La2NiMnO6 epitaxial thin films prepared by polymer-assisted deposition (PAD) and crystallized by rapid thermal annealing (RTA). It is found that samples prepared by RTA have similar values of saturation magnetization and Curie temperature to their counterparts prepared by using conventional thermal annealing (CTA) processes, thus indicating low influence of the heating rates on the B-B' site cationic ordering of the A2BB'O6 double perovskite structure. However, a deeper analysis of the magnetic behavior suggested some differences in the actual microstructure of the films.

Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON2.

Non-centrosymmetric polar compounds have important technological properties. Reported perovskite oxynitrides show centrosymmetric structures, and for some of them high permittivities have been observed and ascribed to local dipoles induced by partial order of nitride and oxide. Reported here is the first hexagonal perovskite oxynitride BaWON2 , which shows a polar 6H polytype. Synchrotron X-ray and neutron powder diffraction, and annular bright-field in scanning transmission electron microscopy indicate that it crystalizes in the non-centrosymmetric space group P63 mc, with a total order of nitride and oxide at two distinct coordination environments in cubic and hexagonal packed BaX3 layers. A synergetic second-order Jahn-Teller effect, supported by first principle calculations, anion order, and electrostatic repulsions between W6+ cations, induce large distortions at two inequivalent face-sharing octahedra that lead to long-range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity.

Aqueous Chemical Solution Deposition of Functional Double Perovskite Epitaxial Thin Films.

Double perovskite structure (A2 BB'O6 ) oxides exhibit a breadth of multifunctional properties with a huge potential range of applications in fields as diverse as spintronics, magneto-optic devices, or catalysis, and most of these applications require the use of thin films and heterostructures. Chemical solution deposition techniques are appearing as a very promising methodology to achieve epitaxial oxide thin films combining high performance with high throughput and low cost. In addition, the physical properties of these materials are strongly dependent on the ordered arrangement of cations in the double perovskite structure. Thus, promoting spontaneous cationic ordering has become a relevant issue. In this work, our recent achievements by using polymer-assisted deposition (PAD) of environmentally friendly, water-based solutions for the growth of epitaxial ferromagnetic insulating double perovskite La2 CoMnO6 and La2 NiMnO6 thin films on SrTiO3 and LaAlO3 single-crystal substrates are presented. It is shown that the particular crystallization and growth process conditions of PAD (very slow rate, close to thermodynamic equilibrium conditions) promote high crystallinity and quality of the films, as well as favors spontaneous B-site cationic ordering.

Appraisal of calcium ferrites as cathodes for calcium rechargeable batteries: DFT, synthesis, characterization and electrochemistry of Ca4Fe9O17.

Sustainability combined with high energy density prospects makes Fe-based oxides attractive as cathodes for calcium rechargeable batteries. This work presents a DFT evaluation of the CaFe2+nO4+n (0 < n < 3) family, for which both the average intercalation voltage and the theoretical specific capacity decrease with the increasing n value. The term n = 1/4, Ca4Fe9O17, meets the most appealing characteristics: a calculated average voltage of 4.16 V, a theoretical specific capacity of 230 mA h g-1 and the lowest energy barrier for Ca migration so far predicted for an existing oxide (0.72 eV). To overcome the previously reported synthesis difficulties, we employed a novel synthesis procedure in sealed quartz tubes followed by quenching in water. The XRD and SAED patterns of the prepared Ca4Fe9O17 powder reveal a certain degree of stacking defects along the c axis. Attempts to deinsert Ca ions from Ca4Fe9O17 by chemical means (NO2BF4 in ACN) and in electrochemical Ca cells were unsuccessful, although some hints of oxidation are observed in Li cells with the LP30 electrolyte. The suitability of Ca4Fe9O17 as a Ca cathode is pending further studies utilizing Ca-electrolytes with high anodic stability.

On the Study of Ca and Mg Deintercalation from Ternary Tantalum Nitrides.

Layered CaTaN2 and MgTa2N3 and cubic Mg2Ta2N4 were prepared by direct solid state reaction from the binary nitrides Ta3N5 and A3N2 (A: Mg, Ca). CaTaN2 showed a slight Ca deficiency (0.11 moles per formula), and a monoclinic distortion from previously reported R3̅m symmetry, with space group C2/m and cell parameters a = 5.4011(2), b = 3.1434(1), c = 5.9464(2) Å and ß = 107.91(3)°. Ca2+ and Mg2+ deintercalation was investigated in the three compounds both chemically and electrochemically. No significant Mg2+ extraction could be inferred for MgTa2N3 and Mg2Ta2N4, neither after reaction with NO2BF4 nor after electrochemical oxidation at 100 °C in alkyl carbonate electrolytes. Rietveld refinement of the X-ray powder diffraction pattern of chemically oxidized Ca0.89TaN2 indicates a decrease of the Ca content to 0.34 concomitant to the disappearance of the monoclinic distortion and expansion of the interlayer space from 5.658 to 5.762 Å, space group R3̅m and cell parameters a = 3.1103(1) and c = 17.287(1) Å. Deintercalation in this compound was also achieved electrochemically at 100 °C. Results of density functional theory calculations seem to indicate that reaction mechanisms for CaTaN2 oxidation additional and/or alternative to deintercalation are taking place, which is likely related to the loss of crystallinity observed upon oxidation and the irreversibility of the process.

Crystal Growth Mechanisms of BiFeO3 Nanoparticles.

A wet-chemical synthesis process was designed to obtain reproducible single-phase multiferroic BiFeO3 nanoparticles. The phase purity, single crystallinity, and size of the nanoparticles are confirmed through the analysis of X-ray diffraction patterns, Raman spectroscopy, and high resolution transmission electron microscopy experiments. Crystal nucleation happens within the amorphous-rich area in multiple seeds, leading to the formation of single crystalline nanoparticles with no preferential faceting. Crystallization mechanisms of BiFeO3 nanoparticles were investigated following the Kissinger-Akahira-Sunose approach, indicating that two crystallization steps are responsible of the complete BiFeO3 nanoparticle formation. The first crystallization step involves a maximum of 70% of the final crystal volume, arising from nanocrystal nucleation and growth. The second step occurs above this threshold crystal volume fraction, and it is related to the nanocrystallite coalescence process. Analysis of the thermodynamic process of the crystallization of BiFeO3 nanoparticles following Ostwald rules suggests a relatively low energy barrier for crystal nucleation, highlighting that phase pure, single crystalline BiFeO3 nanoparticles are obtained using the present optimized wet-chemical synthesis process, with temperatures as low as 450 °C.

Topochemical nitridation of Sr2FeMoO6.

The topotactic nitridation of cation ordered, tetragonal Sr2FeMoO6 in NH3 at moderate temperatures leads to cubic, Fm3[combining macron]m double perovskite oxynitride Sr2FeMoO4.9N1.1 where double-exchange interactions determine ferromagnetic order with TC ≈ 100 K. Substitution of oxide by nitride induces bond asymmetries and local electronically driven structural distortions, which combined with Fermi level lowering restricts charge itinerancy to confined regions and preclude spontaneous long-range magnetic order. Under a magnetic field, ferromagnetic correlations expand, favoring charge delocalization and a negative magnetoresistance is observed.

Electrochemical calcium extraction from 1D-Ca3Co2O6.

The electrochemical oxidation of a transition metal oxide through calcium extraction is achieved for the first time. The 1D framework of Ca3Co2O6 is maintained upon oxidation and the new phase formed exhibits a modulated structure. The process occurs at high potential and is partially reversible, which opens prospects for a calcium battery proof-of-concept.

Confinement generates single-crystal aragonite rods at room temperature.

The topic of calcite and aragonite polymorphism attracts enormous interest from fields including biomineralization and paleogeochemistry. While aragonite is only slightly less thermodynamically stable than calcite under ambient conditions, it typically only forms as a minor product in additive-free solutions at room temperature. However, aragonite is an abundant biomineral, and certain organisms can selectively generate calcite and aragonite. This fascinating behavior has been the focus of decades of research, where this has been driven by a search for specific organic macromolecules that can generate these polymorphs. However, despite these efforts, we still have a poor understanding of how organisms achieve such selectivity. In this work, we consider an alternative possibility and explore whether the confined volumes in which all biomineralization occurs could also influence polymorph. Calcium carbonate was precipitated within the cylindrical pores of track-etched membranes, where these enabled us to systematically investigate the relationship between the membrane pore diameter and polymorph formation. Aragonite was obtained in increasing quantities as the pore size was reduced, such that oriented single crystals of aragonite were the sole product from additive-free solutions in 25-nm pores and significant quantities of aragonite formed in pores as large as 200 nm in the presence of low concentrations of magnesium and sulfate ions. This effect can be attributed to the effect of the pore size on the ion distribution, which becomes of increasing importance in small pores. These intriguing results suggest that organisms may exploit confinement effects to gain control over crystal polymorph.