Double Perovskite Oxides Research Articles

Preparation and Properties of Fe-Based Double Perovskite Oxide as Cathode Material for Intermediate-Temperature Solid Oxide Fuel Cell

Double perovskite oxides with mixed ionic and electronic conductors (MIECs) have been widely investigated as cathode materials for solid oxide fuel cells (SOFCs). Classical Fe-based double perovskites, due to their inherent low electronic and oxygen ionic conductivity, usually exhibit poor electrocatalytic activity. The existence of various valence states of B-site ions modifies the material’s catalytic activity, indicating the possibility of the partial substitution of Fe by higher-valence ions. LaBaFe2−xMoxO5+δ (x = 0, 0.03, 0.05, 0.07, 0.1, LBFMx) is used as intermediate-temperature solid oxide fuel cell (IT-SOFC) cathode materials. At a doping concentration above 0.1, the Mo substitution enhanced the cell volume, and the lattice expansion caused the formation of the impurity phase, BaMoO4. Compared with the parent material, Mo doping can regulate the oxygen vacancy concentration and accelerate the oxygen reduction reaction process to improve the electrochemical performance, as well as having a suitable coefficient of thermal expansion and excellent electrode stability. LaBaFe1.9Mo0.1O5+δ is a promising cathode material for IT-SOFC, which shows an excellent electrochemical performance, with this being demonstrated by having the lowest polarization resistance value of 0.017 Ω·cm2 at 800 °C, and the peak power density (PPD) of anode-supported single-cell LBFM0.1|CGO|NiO+CGO reaching 599 mW·cm−2.

Observation of Griffiths phase and giant magnetocaloric effect in double perovskite oxide RE2FeCrO6 (RE = Gd, Tb, Dy, Er)

AbstractThe magnetic properties of double perovskite oxide RE2FeCrO6 (RE = GD, Tb, Dy, Er) were systematically studied, and the Griffiths phase evolution was observed. In Tb2FeCrO6, Dy2FeCrO6, and Er2FeCrO6, there are antiferromagnetic (AFM)‐ferromagnetic (FM) first‐order phase transition and the Griffiths phase with coexistence of FM and paramagnetic (PM) was observed by the EPR spectra. Gd2FeCrO6 has an AFM–PM second‐order phase transition, and there is no first‐order phase transition in the range of ∆H = 0–50 kOe. As the temperature decreases, all four sets of samples present χ−1 (T) deviates downwards from the Curie–Weiss linear behavior from 0.2 to 5 kOe, corresponding to the typical characteristics of Griffiths phase evolution. In addition, all four sets of samples have excellent magnetocaloric performance. Especially, the Gd2FeCrO6 oxide has giant magnetic entropy change and relative cooling power (−∆SMmax = 30.31 J/kg K and RCP = 312.8 J/kg when ∆H = 50 kOe). From the perspective of low‐temperature magnetic refrigeration application, the present work provides important candidate references for magnetic component researchers.

Evolution of metallicity, enhancement of [formula omitted] and magnetic anisotropy energy in Y[formula omitted]NiIrO[formula omitted]: Hydrostatic ([111]) strain influence

Ir-based double perovskite oxides (DPO) provide a distinct electronic and magnetic behavior due to entanglement among lattice distortion, strong electron correlation, and spin–orbit coupling (SOC). In this work, we investigated the hydrostatic ([111]) strain impact on the physical properties of the Y2NiIrO6 DPO using ab-initio calculations. Unstrained motif displayed the ferrimagnetic (FiM) spin state owing to strong antiferromagnetic (AFM) interactions between Ni↑ and Ir↓ ions, further confirmed by the computed partial spin magnetic moments and 3D spin-magnetization density iso-surfaces plots. A Mott-insulating state is established with an energy band gap (Eg) of 0.43 eV due to the existence of a rare Ir+4 state having Jeff.=12 and a Curie temperature (TC) of 198 K using the Heisenberg Hamiltonian model, which is up to the experimental observations. The easy magnetic axis is the [010] (b-axis) having a giant magnetic anisotropy energy (MAE) constant of 1.7 × 108 erg/cm3. Moreover, it is predicted that strain holds the FiM spin order as a magnetic ground state for the considered range of ±8%. Notably, an electronic transition from Mott-insulating to a metallic state is established at a critical compressive strain of −8%, where the admixture of Ir 5d states appears at/around the Fermi level. On the other hand, Eg solely increases with the increase of tensile strain amplitude. Due to strong and weak hybridization, the spin/orbital magnetic moment value is reduced and enhanced as a function of compressive and tensile strains, respectively. Along with this, it is found that MAE/TC increases to 25%/18% and 15%/10% at −8% compressive and ＋8% tensile strains due to larger structural distortion than that of the unstrained one, which enhances the system potential for magnetic memory devices.

Mixed Conduction in A-Site Double-Perovskite Na1+xLa1-xZr2O6-δ Proton Conductors.

Perovskite-type proton conductors exist in two structural forms, ABO3 and A2B'B″O6. In this study, novel A-site double-perovskite proton conductors (A'A″B2O6) were proposed. Na1+xLa1-xZr2O6-δ (x = 0, 0.1, 0.2) perovskites were prepared by a solid-state reaction at 1200 °C. However, raising the sintering temperature to 1300 °C resulted in the Na to volatilize, converting the Na1.1La0.9Zr2O6-δ into La0.9Zr2O6-δ. The conductivities of these materials in a humid atmosphere were tested using electrochemical impedance spectroscopy, and their carrier transport numbers were measured using the defect equilibria model and concentration cell method. Na1.1La0.9Zr2O6-δ and Na1.2La0.8Zr2O6-δ are predominantly proton conductors, with Na1.1La0.9Zr2O6-δ exhibiting the highest proton transport number of 0.52 at 800 °C. In contrast, NaLaZr2O6 is predominantly an electronic conductor, while La0.9Zr2O6-δ functions as an oxide ion conductor. Due to their high protonic transport numbers, these Na1+xLa1-xZr2O6-δ A-site double-perovskite oxides present a promising avenue for the development of proton conductors.

A‐site Regulated (PrBa)xCo1.5Fe0.5O6‐δ Double Perovskite Oxides: Highly Active and Durable Electrocatalysts for the Enhanced Oxygen Evolution Reaction

Oxygen evolution reaction (OER) represents a significant bottleneck in many energy technologies such as electrochemical water splitting, metal‐oxygen (O) batteries, and solid oxide fuel cells (SOFCs), because of the complexity of the reaction process. Double perovskite oxides (ABO3), recognized for their compositional flexibility, have emerged as excellent OER activity and stability. This study investigates the catalytic potential of B‐site ordered double ABO3 with (PrBa)xCo1.5Fe0.5O6‐δ (PBCF‐x, x=0.9‐1.1) in alkaline media. The results reveal that PBCF‐0.9, characterized by an A‐site deficient composition, exhibits exceptional OER activity. It demonstrates a low Tafel slope of 76.12 mV⋅dec‐1 and a low overpotential (η) of 270 mV at 10 mA⋅cm‐2. Notably, the intrinsic OER activity of PBCF‐0.9 is 25% higher than that of the stoichiometric PBCF‐1.0. Additionally, PBCF‐0.9 exhibits remarkable durability, as evidenced by its stable performance during a 6‐hour chronopotentiometry (CP) test and minimal microstructural changes. These results underscore the effectiveness of A‐site deficiency in optimizing the structure of double ABO3 for improved OER performance. This approach presents a promising strategy for designing highly efficient, stable, and inexpensive catalysts for energy‐related applications.

Observation of Enhanced Long-Range Ferromagnetic Order in B-Site Ordered Double Perovskite Oxide Cd2CrSbO6.

A B-site ordered double perovskite oxide Cd2CrSbO6 was synthesized under high-pressure and high-temperature conditions. The compound crystallizes to a monoclinic structure with a space group of P21/n. The charge configuration is confirmed to be that of Cd2+/Cr3+/Sb5+. The magnetic Cr3+ ions form a tetrahedral structural frustrated lattice, while a long-range ferromagnetic phase transition is found to occur at TC = 16.5 K arising from the superexchange interaction via the Cr-O-Cd-O-Cr pathway. Electrical transport measurements indicate that Cd2CrSbO6 is an insulator that can be described by the Mott 3D variable range hopping mechanism. First-principles calculations reproduce well the ferromagnetic and insulating ground state of Cd2CrSbO6 with an energy band gap of 1.55 eV. The intrinsic ferromagnetic insulating nature qualifies Cd2CrSbO6 as a promising candidate for possible spintronics applications.

Polar phonons features and intrinsic dielectric properties of RE2CoMnO6 (RE = Tb, Dy, Ho, Tm and Yb) double perovskites

RE-based double perovskite (DP) oxides of the RE₂TMTM'O₆ family exhibit intriguing magnetodielectric (MD) properties and magnetocaloric effects (MCEs), making them promising candidates for applications in high-performance supercapacitors, memories, spintronic devices, and cryogenic magnetic refrigeration. This paper addresses the vibrational properties of RE2CoMnO6 (RE = Tb, Dy, Ho, Tm, and Yb) ceramics for the first time using infrared reflectance spectroscopy. The dielectric merit factors in the microwave (MW) range, including the quality factor (Qu) and the static dielectric constant (ɛ0), were estimated. It was observed that the intrinsic dielectric constants decrease from approximately 26.2 to 14.4 as the rare earth ionic radius decreases. The mean values of these compounds suggest their suitability for applications in MW circuitry devices.

Narrow Band Gap Base Metal Double Perovskite Oxides Through Copper Doping of Ba2Ca0.66Nb1.33O6

This work examines the influence of copper doping on the structure, optoelectronic properties, and photocatalytic performance of transition metal double perovskite oxides of the Ba2Ca0.67Nb1.33O6 (BCN) family. A solid-state synthesis method was used to achieve partial substitution of Cu2+ in the Nb5+ site (Ba2Ca0.67Nb1.33-xCuxO6-δ, x = 0.05, 0.13, 0.26) and Ca2+ site (Ba2Ca0.67-xCuxNb1.33O6-δ, x = 0.13). The incorporation of copper in BCN resulted in significant changes in the structure and optoelectronic properties. Major differences were observed when Cu atoms occupied the Nb-site versus the Ca-site. The parent compound and Ca-site doped compounds crystallized in a P3 1 space group while Nb-site doped compounds showed increasing Fm3 mixed phase character. Cu doping resulted in a dramatic shift of the absorption band edge towards the visible region. Ca-site doping resulted in a primary band edge shift from 3.8 eV to 2.1. For the Nb-site doped compounds, the primary band-edge remained at 3.8 eV but a secondary band-edge appeared which progressively shifted to smaller energies as Cu doping increased. Ba2Ca0.67Nb1.20Cu0.13O6-δ and Ba2Ca0.67Nb1.07Cu0.26O6-δ exhibited strong absorption of near-infrared photons of wavelength well beyond 800 nm. The double perovskite oxides were utilized as photoanodes for photoelectrochemical water splitting, exhibiting both a visible photoresponse (until wavelengths as low as 520 nm) and good photochemical stability. This work showcases the possibility of forming new low band gap multi-element inorganic semiconductor oxides constituted entirely of base metals and oxygen.

Characterization of A-site doped PrBaCo2O5+δ perovskites as cathode materials for IT-SOFCs

Creating highly efficient and durable cathodes persists as a formidable task in the realm of intermediate temperature solid oxide fuel cells (IT-SOFCs). Hence, we present a double perovskite oxide, Pr0.6Sr0.4BaCo2O5+δ (PS0.4BC), and its electrocatalytic activity is thoroughly investigated. The XRD test is carried out and a notable transformation in the phase structure is observed upon the introduction of Sr2+ ions into the PBC matrix. That is, the phase structure of the material changes from double perovskite structure to single perovskite structure. Through the TG and TEC test that the introduction of Sr2+ ions into the lattice can create additional sites for oxygen vacancy formation and reduce TEC values. Further verify that Sr doping can enhance the concentration of oxygen vacancies of the material. The PS0.4BC cathode material exhibits remarkably low polarization resistance, achieving an impressive value of 0.027 Ω cm2 at an operating temperature of 800 °C. Oxygen partial pressure test shows that as the oxygen partial pressure decreases, there is a notable increase in impedance, particularly evident in the low frequency region of the Nyquist plots. This indicates that the oxygen content has obvious effects on the low-frequency processes. When the oxygen partial pressure exceeds 0.05 atm, the oxygen adsorption-dissociation and diffusion process is the rate-limiting step in the ORR. However, when the oxygen partial pressure is less than 0.05 atm, the formation of lattice oxygen through the combination of oxygen ions and oxygen vacancies processes is the rate-limiting step. Compared PBC cathode material, the more pronounced changes in the high frequency arc of the PS0.4BC cathode at the same oxygen content. It shows that Sr doping significantly changes the high frequency process. After doping, the oxygen vacancy concentration increases, which facilitates the occurrence of the charge transfer process at high frequency.

Investigation of the structural, electronic, magnetic, and optical properties of the double perovskite oxide semiconductor La2NiMnO6: Ab initio calculations by using GGA-PBE and GGA + mBJ approximations

In this paper, we examined the La2NiMnO6 double perovskite oxide semiconductor materials, our treatment included the structural, electronic, magnetic, and optical characteristics by utilizing the density functional theory, which was performed in the Wien2k software. The exchange–correlation potential was carried out in combination with the GGA-PBE (Perdew Burke Ernzerhof Generalized Gradient Approximation), and GGA + mBJ (modified Becke and Johnson) was used for the exchange–correlation potentials. The results suggest that the compound La2NiMnO6 exhibits in a ferrimagnetic state. It was also found that the stable ground state of the compound is ferrimagnetic. The results demonstrate that La2NiMnO6 has a band gap whose spin-up value is 0 eV and spin-down (dn) value is 2.86 eV (GGA-PBE), with up values is 0 eV and dn value being of 3 eV (GGA + mBJ). We also explored different optical properties, among them electron energy loss, absorption coefficient, real and imaginary dielectric tensor, and real and imaginary optical conductivity.

A comparative study of influence of isovalent and aliovalent A-site substitutions on the structural, magnetic, and dielectric properties of Sr2CrMoO6 double perovskites

We report on a comparative study of the structural, magnetic, and dielectric and properties of isovalent and aliovalent A-site substituted Sr2-xAxCrMoO6 (A = Ca, x = 0.0, 0.1, 0.3, 0.5, 0.7, 0.8, 1.0; A = K, La only x = 0.5) double perovskites, which were synthesized via sol-gel process. X-ray diffraction patterns and Rietveld refinements demonstrated that all the Sr2-xAxCrMoO6 powders crystallized in a cubic crystal structure with space group of Fm3‾m. SEM images revealed that the Sr2-xAxCrMoO6 powders exhibited a spherical morphology. Their chemical compositions were determined by quantitative energy dispersive X-ray spectroscopy, which were close to the nominal values. FTIR spectra analyses verified the presence of (Cr, Mo)O6 octahedra in these powders. XPS spectra validated the existence of Sr2+, K+, Ca2+, La3+, and Cr3+ ions in the powders, and oxygen existed in the forms of lattice oxygen and absorbed oxygen respectively, whereas Mo element had a mixed chemical valence state of Mo4+ and Mo6+. The Sr2CrMoO6 (SCMO) powders had a saturation magnetization (MS) of 0.016 μB/f.u. at 2 K, magnetic Curie temperature (TC) of 337 K, and irreversibility temperature (Tirr) of 329 K where the zero-field cooled (ZFC) and field-cooled (FC) magnetization (MZFC and MFC, respectively) curves became bifurcated. A spin-glass behavior was observed at temperature (TB) of 81 K. Both Tirr and TB shifted towards low temperature with increasing the external magnetic field. In addition, the MZFC and MFC curves became almost overlapped under the external field of 50 kOe, and the spin-glass behavior disappeared. The M-H data demonstrated that both isovalent and aliovalent A-site substitutions could improve the magnetic properties and B-site ordering degree (η) of the SCMO powders. However, isovalent Ca-substitution exhibited more significant enhanced effect on the magnetic properties in comparison with the aliovalent A-site substitutions either by K- or La-substitution. Among the isovalent Ca-substituted Sr2-xCaxCrMoO6 (x = 0.1–1.0) powders, Sr1.2Ca0.8CrMoO6 sample had a maximum MS value of 0.64 μB/f.u. at 2 K, over 30 times enhancement of that of the pristine SCMO powders. The Sr2-xAxCrMoO6 ceramics exhibit a strong frequency dependent dielectric behavior, which can be well interpreted by Maxwell-Wagner relaxation model. The anomalous dielectric relaxor behavior of the SCMO ceramics observed at 260 K was ascribed to the jumping of the electrons trapped in a shallower energy level created by oxygen vacancies. The dielectric constant of the isovalent Ca-substituted Sr1.5Ca0.5CrMoO6 samples was 30 times larger than that of the pristine SCMO samples. Our present results demonstrate that isovalent Ca-substitution at A-site could improve the magnetic and dielectric properties of the sol-gel derived SCMO double perovskite oxides, which have potential applications in the fields of spintronic devices and dielectric devices.

Structural and Magnetic Properties of B-Site-Ordered RE2CuTiO6 (RE = Dy, Ho, and Er) Double-Perovskite Oxides with Significant Cryogenic Magnetocaloric Performance.

The magnetocaloric effect (MCE) is currently intensively investigated in various rare earths (RE)-containing magnetic solids, not only for developing appropriate magnetocaloric materials (MCMs) for cryogenic magnetic cooling but also for deepening our understanding into the inherent physical properties of these materials. Here, we provide a systematic experimental investigation into a series of new RE2CuTiO6 (RE = Dy, Ho, Er) double-perovskite (DP) oxides regarding the structural and magnetic properties, especially for their cryogenic MCE and magnetic-phase transition (MPT). All of these RE2CuTiO6 oxides crystallize in a B-site-ordered hexagonal DP-type structure with the symmetry of the crystallographic space group P6̅m2. These DP oxides exhibit magnetic ordering, with MPT temperatures of approximately 2.7, 2.2, and 2.7 K for Dy2CuTiO6, Ho2CuTiO6, and Er2CuTiO6, respectively. The magnetocaloric performances of the RE2CuTiO6 DP oxides were characterized by the peak values of magnetic entropy change, the temperature-averaged magnetic entropy change (5K-lift), and relative cooling powers. These magnetocaloric parameters were deduced to be 18.7/17.9 J/kgK and 298.2 J/kg for Dy2CuTiO6, 12.5/12.2 J/kgK and 273.9 J/kg for Ho2CuTiO6, and 13.8/12.9 J/kgK and 188.4 J/kg for Er2CuTiO6 under a magnetic field change of 0-5 T. These values are comparable to those of most reported RE-containing magnetocaloric materials, indicating that these RE2CuTiO6 DP oxides are promising candidates for cryogenic magnetic cooling applications.

Optimizing Reversible Exsolution and Phase Transformation in Double Perovskite Sr2Fe1.5-xCoxMo0.5O6-δ Electrodes for High-Performance Symmetric Solid Oxide Cells.

Double perovskite (DP) oxides are promising electrode materials for symmetric solid oxide cells (SSOCs) due to their excellent electrochemical activity and stability. B-site cation doping in DP oxides affects the reversibility ofphase transformation and exsolution, which plays a crucial role in the catalyst recovery. Yet, few studies have been conducted on this topic. In this study, the Sr2Fe1.5-xCoxMo0.5O6-δ (CSFM, x = 0, 0.1, 0.3, 0.5) DP system demonstrates modulated exsolution and phase transformation reversibility by manipulating the oxygen vacancy concentration. The correlation between Co-doping level and oxygen vacancy concentration is investigated to optimize the exsolution and phase transformation properties. Sr2Fe1.2Co0.3Mo0.5O6-δ (3CSFM) exhibits reversible transformation between DP and Ruddlesden-Popper phases with a high density of exsolved CoFe nanoparticles under redox atmospheres. The quasi-symmetric cell with 3CSFM shows a peak power density of 1.27Wcm-2 at 850°C in H2 fuel cell mode and a current density of 2.33Acm-2 at 1.6V and 800°C in H2O electrolysis mode. The 3CSFM electrode exhibits robust stability during continuous operation for ≈700h. These results demonstrate the significant role of B-site doping in designing DP materials capable of dynamic phase transformation in diverse environments.

Pressure-induced softening in bulk modulus due to magnetoelastic coupling in Nd2CoFeO6 double perovskite

In the present work, we have investigated the structural response of transition metal double perovskite oxide Nd2CoFeO6 under pressure by XRD and Raman spectroscopic measurements. From XRD data, we have observed a pressure-induced structural transition from the orthorhombic phase to the monoclinic phase at about 14.8 GPa. An anomalous increase in compressibility at a much lower pressure (∼1.1 GPa) is seen where no structural transition occurs. At about the same pressure, a sudden drop in the slope of the Raman shift is observed. Further investigation at low temperatures reveals that the B1g Raman mode is strongly affected by magnetic interactions. Additional high-pressure Raman experiments with the application of a magnetic field have indicated that the mentioned anomaly around 1.1 GPa can be explained by a high-spin to low-spin transition of Co3+.

Origin of Magnetism in a Supposedly Nonmagnetic Osmium Oxide.

A supposedly nonmagnetic 5d^{1} double perovskite oxide is investigated by a combination of spectroscopic and theoretical methods, namely, resonant inelastic x-ray scattering, x-ray absorption spectroscopy, magnetic circular dichroism, and multiplet ligand-field calculations. We found that the large spin-orbit coupling admixes the 5d t_{2g} and e_{g} orbitals, covalency raises the 5d population well above the nominal value, and the local symmetry is lower than O_{h}. The obtained electronic interactions account for the finite magnetic moment of Os in this compound and, in general, of 5d^{1} ions. Our results provide direct evidence of elusive Jahn-Teller distortions, hinting at a strong electron-lattice coupling.

Co-free and Sr-free double-perovskite oxide PrBaFe1.9Nb0.1O5+δ as a potential electrode material for symmetrical solid oxide fuel cells

Co-free and Sr-free double-perovskite oxide PrBaFe1.9Nb0.1O5+δ as a potential electrode material for symmetrical solid oxide fuel cells

Enhanced Cryogenic Magnetocaloric Effect from 4f‐3d Exchange Interaction in B‐Site Ordered Gd2CuTiO6 Double Perovskite Oxide

AbstractMagnetic refrigeration based on the principle of the magnetocaloric effect (MCE) in magnetic solids has been considered as a prospective cooling technology. Exploring suitable magnetocaloric materials (MCMs) is a vital prerequisite for practical applications. Herein, an excellent cryogenic MCM—the B‐site‐ordered Gd2CuTiO6 double perovskite (DP) oxide—which exhibits the largest MCE among known Gd‐based DP oxides, is identified. Such enhanced cryogenic MCE in the Gd2CuTiO6 DP oxide likely stems from the exchange interaction effect between Gd‐4f and Cu‐3d magnetic sublattices. Under a magnetic field change of 0–7 T, the maximum magnetic entropy change (−ΔSTmax) of the Gd2CuTiO6 DP oxide reaches 51.4 J kg−1 K−1 (378.2 mJ cm−3 K−1), which is much larger than that of the commercialized magnetic refrigerant Gd3Ga5O12, which is 38.3 J kg−1 K−1 (271.2 mJ cm−3 K−1), and it is also superior to most of the recently reported benchmarked cryogenic MCMs, indicating the possibility for practical applications. This work also provides a productive route for future cryogenic MCM design by harnessing 4f–3d exchange interactions.

B-site Doping Boosts the OER and ORR Performance of Double Perovskite Oxide as Air Cathode for Zinc-Air Batteries.

Double perovskite oxides are key players as electrocatalytic oxygen catalysts in alkaline media. In this study, we synthesized B-site doped NdBaCoaFe2-aO5+δ (a= 1.0, 1.4, 1.6, 1.8) electrocatalysts, systematically to probe their bifunctionality and assess their performance in zinc-air batteries as air cathodes. X-ray photoelectron spectroscopy analysis reveals a correlation between iron reduction and increased oxygen vacancy content, influencing electrocatalyst bifunctionality by lowering the work function. The electrocatalyst with highest cobalt content, NdBaCo1.8Fe0.2O5+δ exhibited a bifunctional index of 0.95 V, outperforming other synthesized electrocatalysts. Remarkably, NdBaCo1.8Fe0.2O5+δ, demonstrated facilitated charge transfer rate in oxygen evolution reaction with four-electron oxygen reduction reaction process. As an air cathode in a zinc-air battery, NdBaCo1.8Fe0.2O5+δ demonstrated superior performance characteristics, including maximum capacity of 428.27 mA h at 10 mA cm-2 discharge current density, highest peak power density of 64 mW cm-2, with an outstanding durability and stability. It exhibits lowest voltage gap change between charge and discharge even after 350 hours of cyclic operation with a rate capability of 87.14%.

Physical properties of novel double perovskite oxides Ba2XSbO6(X = P, As) by first-principle calculations

In this article, the structural, mechanical, electronic, optical, thermal, and thermodynamic properties of Ba2XSbO6 (X=P, As) double perovskite oxides were investigated by using first-principles calculations. The results show that the Goldsmith’s tolerance factor and octahedral factor of the two perovskites are in a stable range, the binding energy and formation energy are negative, and the elastic constants meet the Born-Huang stability criterion. These results suggest the stability of the two perovskite oxides. The mechanical property study indicates that Ba2XSbO6 (X=P, As) exhibits high bulk modulus and shear modulus. Poisson’s ratio (ν) and the elastic anisotropy index (A) suggest that they are anisotropic ductile materials. The electronic properties show that Ba2PSbO6 and Ba2AsSbO6 are indirect bandgap semiconductors with bandgap values of 2.130 eV and 1.596 eV, respectively. The optical properties show that Ba2XSbO6 (X=P, As) has excellent light absorption capacity in the range of 2.5–30 eV. Specifically, Ba2AsSbO6 has a higher absorption capacity for visible light compared to Ba2PSbO6. Thermodynamic properties show that the Debye temperature of the two perovskites is higher than 420 K, the melting points is higher than 1700 K, the minimum lattice thermal conductivities is close to 1, and the specific heat reaches the Dulong-Petit limit at about 700 K. This study shows that the double perovskite oxide Ba2XSbO6 (X=P, As) has important potential in the field of thermoelectricity and optoelectronics.

Advancing Solid Oxide Fuel Cell Performance: Enhanced Electrochemical Properties of Pr1-xCaxBaFe2O5+δ Nanofiber Cathodes via Ca Doping.

The double perovskite oxide PrBaFe2O5+δ has great potential as a cathode material for solid oxide fuel cells (SOFCs). However, the electrochemical characteristics of Fe-based double perovskites are relatively inferior. To improve its electrochemical performance, Ca is investigated to partially replace Pr, forming Pr1-xCaxBaFe2O5+δ (PCBFx, x = 0.0-0.3) by an electrospinning technique. The PCBFx nanofibers exhibited a crystalline structure characterized by orthorhombic symmetry and space group P4/mmm. Furthermore, these PCBFx nanofibers displayed exceptional chemical compatibility with the Sm0.2Ce0.8O1.95 (SDC) electrolyte when sintered at a temperature of 900 °C for 5 h. The X-ray photoelectron spectroscopy (XPS) analysis reveals a progressive increase in the Fe4+ concentration as the Ca doping level rises. The polarization resistances (Rp) of the PCBF00, PCBF01, PCBF02, and PCBF03 nanofiber cathodes were 0.103, 0.079, 0.056, and 0.048 Ω cm2 at 750 °C. In the meantime, doping Ca increases the peak power density of the single cell by 46%, from 762.80 (PCBF00) to 1114.85 (PCBF03) mW cm-2 at 750 °C. The results demonstrate that PCBF03 double perovskite nanofibers exhibit great potential as cathode materials for SOFCs.