Vanadium Doping Research Articles

Effect of vanadium doping on electrochemical properties of lithium iron manganese phosphate

Abstract The low-cost lithium iron manganese phosphate anode material has a 15% higher energy density than lithium iron phosphate, and it has received wide attention in recent years. However, the poor electronic/ionic conductivity of lithium ferromanganese phosphate leads to poor power performance, which makes it difficult to meet the needs of practical applications. In this study, a V-doped LiMn0.2Fe0.8PO4(LFMP) material is designed and prepared, and every particle is coated by a uniform carbon layer. The V-doped LFMP material shows better rate performance and cycle performance. When the optimal vanadium doping amount is 0.01, the specific discharge capacity of the material is 164.0 mAh/g at 0.1 C.

Vanadium-doped FeO/NiS nanosheet arrays: Synergistic heterometal doping and heterostructure design for enhanced oxygen evolution catalysis

The quest for high-performance OER electrocatalysts has been a focal point in the field of energy conversion and storage. Despite the promise shown by nickel sulfide-based materials, the enhancement of their catalytic activity through singular strategies has been found to be inadequate for achieving the desired comprehensive performance improvements. In this context, we introduce a novel V-doped FeO/NiS nanosheet array (V-FeO/NiS/NF) synthesized through a synergistic approach involving heteroatom doping and heterostructure engineering. This advanced material exhibits structural integrity, a three-dimensional nanosheet morphology, and superior electrical conductivity, which collectively contribute to its exceptional electrochemical performance. The V-FeO/NiS/NF electrode can reach a current density of 10 mA cm−2 with an impressively low overpotential of 213 mV and sustains its activity for an extended period of 196 hours, surpassing the stability and efficiency of many electrodes. Theoretical insights reveal that vanadium doping significantly lowers the adsorption free energy of key reaction intermediates, thereby facilitating the OER process. This study not only presents a robust and efficient OER electrocatalyst but also paves the way for the design of advanced, cost-effective nickel-based sulfide catalysts through strategic heteroatom incorporation and structural optimization.

Vanadium doped Fe-Mn bimetallic oxides as cathodic materials for boosted heterogeneous electro-Fenton degradation of organic contaminants

The design of cathode materials with both sustainable H2O2 selectivity and accelerated recyclable regeneration remains a challenge for contaminants removal in heterogeneous electro-Fenton (HEF) process. Herein, a series of ternary Fe0.50Mn0.5−δVδOx (δ = 0.005, 0.01, 0.05) metal oxides have been synthesized and employed as cathodic materials for the degradation of various organic contaminants in water matrix. 99.7 % removal rate was achieved for carbamazepine (CBZ) in 60 min with 98.8 % mineralization rate. Simultaneously, the catalyst exhibited outstanding degradation efficiency (96.0–99.7 %) with other pollutants including sulfonamides (SMX), bisphenol A (BPA), 2,4-dichlorophenol (2,4-DPC) and ofloxacin (OFX), demonstrating its potential application. Factors affecting the EF process, including current density, pH, oxygen flow rate and compatibility of inorganic anions were thoroughly evaluated and the degradation mechanism was studied in detail. Density functional theory (DFT) calculations revealed that the improved catalytic efficiency was originated from vanadium doping to access optimized electronic structure, which endows enhanced 2e− ORR selectivity as well as excellent overall performance for the EF process. This work may enrich the study on EF system and offers a promising strategy for contaminants removal with FeMnVO materials in water treatment applications.

Imaging Negative Charge around Single Vanadium Dopant Atoms in Monolayer Tungsten Diselenide Using 4D Scanning Transmission Electron Microscopy.

There has been extensive activity exploring the doping of semiconducting two-dimensional (2D) transition metal dichalcogenides in order to tune their electronic and magnetic properties. The outcome of doping depends on various factors, including the intrinsic properties of the host material, the nature of the dopants used, their spatial distribution, as well as their interactions with other types of defects. A thorough atomic-level analysis is essential to fully understand these mechanisms. In this work, the vanadium-doped WSe2 monolayer grown by molecular beam epitaxy is investigated using four-dimensional scanning transmission electron microscopy (4D-STEM). Through center-of-mass-based reconstruction, atomic-scale maps are produced, allowing the visualization of both the electric field and the electrostatic potential around individual V atoms. To provide quantitative insights, these results are successfully compared to multislice image simulations based on ab initio calculations, accounting for lens aberrations. Finally, a negative charge around the V dopants is detected as a drop in the electrostatic potential, unambiguously demonstrating that 4D-STEM can be used to detect and to accurately analyze single-dopant charge states in semiconducting 2D materials.

Effect of vanadium doping on structural, dielectric, magnetic, and ferroelectric properties of Ba0.95La0.05TiO3 ceramics

The polycrystalline different Ba0.95La0.05Ti1-xVxO3 (where, x = 0.00 to 0.12) ceramics were synthesized using solid-state reaction method. The toroid- and pellet-shaped samples were sintered at 1200°C temperature for 4 h. According to the outcomes of the X-ray diffraction (XRD) investigation, each sample possesses a tetragonal crystal structure that includes a few impurity peaks. Extra Raman modes at 327 cm−1 (for x = 0.06 to 0.12) may be attributed to localized phonon vibrations in the vicinity of a (substitutional) defect or as a result of the relaxation of Raman selection rules due to defect-induced disorder. The density showed a progressive increase as the concentration of V increases, reaching its maximum at the x = 0.06 sample, after which it drops. The x = 0.06 sample displayed the highest bulk density, with a value of ρB = 4.01 g/cm3. Scanning Electron Micrograph (SEM) showed gradual agglomeration of the grain with V-content due to magnetic dipole interaction between one particle and other neighboring particles and exposed the porous nature of the samples. The TEM image demonstrates that the particles are well crystalline. For all of the compositions, the dielectric constant was larger in lower frequency areas and remained constant in higher frequency region. The sample with x = 0.06 showed a maximum dielectric constant of 1140 at 102 Hz. AC conductivity increased with increasing frequency. The Nyquist plot suggested an appearance of grain boundary (bulk) property of the material. The constant value of the real part of complex initial permeability over long range of frequency indicated the magnetic stability of the materials. For ceramics with x = 0.03, the largest real part of the initial permeability of 17.29 is evident. From the M − H loop, at room temperature, feeble ferromagnetism was observed with vanadium substitution in BLT ceramics. It is found that the highest saturation magnetization for the x = 0.03 sample is 2.61 emu/g. For the composition of x = 0.06, the highest polarization of 2.80 μC/cm2 is observed.

(Invited) Bulk Traps in Layered 2D Gate Dielectrics

Ultra-thin ferromagnets, when coupled with magnetoelectric or multiferroic materials, could potentially enable highly energy-efficient electric field control of the magnet for use in nanoelectronic memories. Substitutional doping of magnetic impurities in monolayer transition metal dichalcogenides (TMDs) may be a promising way to create 2D ferromagnets but, according to theoretical calculations, require high doping levels (10-20 %) to achieve above room temperature (RT) Curie temperature. Room-temperature ferromagnetism has been reported for very low doping levels (0.1-1%), in conflict with the theoretical calculations, and always in the presence of high concentrations of defects, making it unclear if the dopants alone are responsible for this ferromagnetism. In this work, we use a combination of molecular beam epitaxy (MBE), plan-view TEM, XRD, XPS, Raman, and magnetometry to study iron and vanadium doping in monolayer WSe2. We show that optimally grown monolayers with up to 35% doping and low defect density show no ferromagnetism. Interestingly, ferromagnetism is observed when these monolayers contain a significant amount of selenium vacancies (Sevac), intentionally created via a post-growth heat treatment process, and magnetism is seen to scale with heating time/vacancy concentration. Moreover, even undoped WSe2 shows similar ferromagnetism for Sevac > 1014 cm-2. This ferromagnetism can later be quenched by filling these vacancies via Se annealing. For films with low Se vacancy concentration, TEM analysis reveals significant clustering of the V and Fe dopants which likely suppresses the ferromagnetism predicted by theory - a problem that has previously plagued III-V based dilute magnetic semiconductors as well. We go so far as to claim that all of the above room-temperature ferromagnetism reports in the literature thus far are due to Se vacancies and not magnetic doping.

Tuning the electronic structure of monolayer MoS2 towards metal like via vanadium doping

Doping of two-dimensional layered semiconducting materials is becoming pivotal in tailoring their electronic properties, enabling the development of advanced electronic and optoelectronic devices, where the selection of dopant is important. Here, we demonstrate the potential of substitutional vanadium (V) doping in monolayer molybdenum disulfide (MoS2) lattice in different extents leading to tunable electronic and optoelectronic properties. We found that low-level V doping (∼1 at.%) induces p-type characteristics in otherwise n-type monolayer MoS2, whereas medium-level doping (∼5 at.%) leads to an ambipolar semiconductor. Degenerately doped MoS2 (∼9 at.%) facilitates a transition from semiconducting towards metallic (metal-like) with reduced electrical resistivity (∼4.5 Ωm of MoS2 to ∼2.2×10−5Ωm), low activation energy for transport (∼11 meV), and electric field independent drain current in field effect transistor–based transfer characteristics. A detailed temperature- and power-dependent photoluminescence study along with density functional theory–based calculations in support unravels the emergence of an excitonic transition at ∼850 nm with its intensity dependent on the amount of vanadium. This study shows the potential of V doping in MoS2 for generating multifunctional two-dimensional materials for next generation electronics, optoelectronics, and interconnects with systematic control over its electronic structure in a wide range. Published by the American Physical Society 2024

Realizing Efficient Activity and High Conductivity of Perovskite Symmetrical Electrode by Vanadium Doping for CO2 Electrolysis.

Solid oxide electrolysis cells (SOECs) show significant promise in converting CO2 to valuable fuels and chemicals, yet exploiting efficient electrode materials poses a great challenge. Perovskite oxides, known for their stability as SOEC electrodes, require improvements in electrocatalytic activity and conductivity. Herein, vanadium(V) cation is newly introduced into the B-site of Sr2Fe1.5Mo0.5O6-δ perovskite to promote its electrochemical performance. The substitution of variable valence V5+ for Mo6+ along with the creation of oxygen vacancies contribute to improved electronic conductivity and enhanced electrocatalytic activity for CO2 reduction. Notably, the Sr2Fe1.5Mo0.4V0.1O6-δ based symmetrical SOEC achieves a current density of 1.56 A cm-2 at 1.5 V and 800 °C, maintaining outstanding durability over 300 h. Theoretical analysis unveils that V-doping facilitates the formation of oxygen vacancies, resulting in high intrinsic electrocatalytic activity for CO2 reduction. These findings present a viable and facile strategy for advancing electrocatalysts in CO2 conversion technologies.

Novel Sol-Gel Synthesis Route for Ce- and V-Doped Ba0.85Ca0.15Ti0.9Zr0.1O3 Piezoceramics.

To meet the current demand for lead-free piezoelectric ceramics, a novel sol-gel synthesis route is presented for the preparation of Ba0.85Ca0.15Ti0.9Zr0.1O3 doped with cerium (Ce = 0, 0.01, and 0.02 mol%) and vanadium (V = 0, 0.3, and 0.4 mol%). X-ray diffraction patterns reveal the formation of a perovskite phase (space group P4mm) for all samples after calcination at 800 °C and sintering at 1250, 1350, and 1450 °C, where it is proposed that both dopants occupy the B site. Sintering studies show that V doping allows the sintering temperature to be reduced to at least 1250 °C. Undoped BCZT samples sintered at the same temperature show reduced functional properties compared to V-doped samples, i.e., d33 values increase by an order of magnitude with doping. The dissipation factor tan δ decreases with increasing sintering temperature for all doping concentrations, while the Curie temperature TC increases for all V-doped samples, reaching 120 °C for high-concentration co-doped samples. All results indicate that vanadium doping can facilitate the processing of BCZT at lower sintering temperatures without compromising performance while promoting thermal property stability.

Electronic structure and delithiation mechanism of vanadium and nickel doped Li2MnPO4F cathode material for lithium-ion batteries

This study calculates the energy band structure and density of states of Lithium manganese fluorophosphate (Li2MnPO4F, a lithium transition metal phosphate compounds) using the first-principles plane-wave pseudopotential approach within the density-functional theory. The model of Li2M0.5Mn0.5PO4F (M = V, Ni) with transition metal doped Mn sites is constructed by using the CASTEP module. The calculation findings indicate that the transition metal doping can regulate the energy band structure of the intrinsic system, and Li2MnPO4F makes the band gap decrease, and the volume increase with the Li ions of being deintercalated, and the electrons can be readily stimulated from the valence band to the conduction band. The findings indicate that Li2MnPO4F is a favorable cathode material for high-voltage lithium ion batteries (LIBs). The introduction of vanadium (V) and nickel (Ni) doping reduces the band gap, facilitating an easier excitation of electrons from the valence band to the conduction band. This study provides a theoretical study of new cathode materials for high performance LIBs.

Ultra‐Broadband Near‐Infrared Luminescence from a Vanadium‐Activated Phosphate Glass

AbstractBroadband near‐infrared (NIR) emitting materials have gained considerable attention for their applications in lighting, displays, sensing, bio‐imaging, and optical amplification. Recently, numerous excellent broadband NIR emitting materials are developed by introducing Cr3+, Bi+, or Ni2+ ions to various hosts. However, there is a notable absence of reports on ultra‐broadband NIR emitters spanning the entire telecommunication window as well as the NIR‐I (700–1000 nm) and NIR‐II (1000–1700 nm) biological windows activated by vanadium ions. Herein, the study presents, for the first time to the best of the knowledge, ultra‐broadband NIR emission ranging from 850 to 1600 nm (peaking at ≈1000 nm) at room temperature in vanadium‐doped phosphate glass. Detailed spectra and microscopic structure analysis reveal that two V3+‐emitting centers predominantly contribute to the ultra‐broadband emission, corresponding to 3T2(3F)→3A2(3F) spin‐allowed and 3T2(3F)→1E(1D) spin‐forbidden electron transitions of tetrahedrally coordinated V3+ ions. Notably, the tunability of NIR emission peak is demonstrated by adjusting the local glass structure or the vanadium doping content. Moreover, glass‐converted light‐emitting diodes (gc‐LEDs) are fabricated from vanadium‐doped glass, and the potential applications are demonstrated. The work opens new avenues for the design and fabrication of broadband NIR‐emitting materials and opto‐electronic devices.

Perfect Spin Filtering, Giant Magnetoresistance, and Rectification Behavior Induced by V‐Doped Zigzag Graphene Nanoribbons

AbstractEmploying the constructs of density functional theory (DFT) and the Nonequilibrium Green's Function (NEGF), the investigation extensively explores the electronic and transport properties of zigzag graphene nanoribbons (ZGNRs) doped with vanadium (V). Notably, this inquiry unveils that strategic doping can transform V‐doped ZGNRs into spintronic nanodevices with distinctive transport attributes. Initially, the simulations showcase remarkably high spin‐filtering efficiencies (SFEs) at certain bias voltages. Furthermore, a giant magnetoresistance (GMR) peaking at 6.87 10 is detected. In conclusion, the examination discerns a spin rectifier that exhibits a significant rectification ratio (RR) of 9.62 10. This research delineates a viable trajectory for the refinement of high‐performance spintronics in ZGNRs via vanadium doping. The implications of this study indicate that the model harbors considerable promise for application in miniature spintronic devices.

Effect of vanadium doping on magnetic properties and photocatalytic activity of magnesium ferrite: Role of surface charge and dyes adsorption

Spinel magnesium ferrite nanoparticles play an important role in a variety of disciplines, particularly in environmental applications as magnetically separable photocatalysts. MgFe2-1.67xVxO4 with x = 0.0, 0.05, 0.10, and 0.20 were synthesized using the combustion method. X-ray diffraction (XRD) indicated that only the cubic spinel ferrite phase with the Fd3m space group was formed in all doped Mg-ferrite. The cell parameter increased at (x = 0.05) and thereafter dropped with increasing vanadium ion concentration. The saturation magnetization (Ms) increased from 26.181 to 28.953 with x = 0.05, then decreased with further doping. Additionally, the band gap energy (Eg) decreased with increasing v-doping; Eg for MgFe2O4 was 1.79 eV and decreased to 1.71 eV at x = 0.20. All the V-doped MgFe2O4 shows an increase in the efficiency of methyl orange photodegradation relative to undoped MgFe2O4. The boosting in photocatalytic activity of V-doped MgFe2O4 due to electron-hole separation, caused by oxygen vacancies. V-doping changes the point of zero charge of ferrite and increase the MO adsorption, consequently, enhances the photocatalytic degradation. V-doped MgFe2O4 has proved to be an effective magnetically separable and easily reusable photocatalyst withstand seven cycles of recyclability using MgFe2-1.67xVxO4 with x = 0.10, and only 4 % loss of its photocatalytic performance.

Effects of Vanadium Doping on the Optical Response and Electronic Structure of WS2 Monolayers

Abstract2D dilute magnetic semiconductors have been recently reported in transition metal dichalcogenides doped with spin‐polarized transition metal atoms, for example vanadium‐doped WS2 monolayers, which exhibit room‐temperature ferromagnetic ordering. However, a broadband characterization of the electronic band structure of these doped WS2 monolayers and its dependence on vanadium concentration is still lacking. Therefore, power‐dependent photoluminescence, resonant four‐wave mixing, and differential reflectance spectroscopies are performed here to study optical transitions close to the A exciton energy of vanadium‐doped WS2 monolayers at three different doping levels. Instead of a single A exciton peak, vanadium‐doped samples exhibit two photoluminescence peaks associated with transitions from a donor‐like level and the conduction band minima. Moreover, resonant Raman and second‐harmonic generation experiments reveal a blueshift in the B exciton energy but no energy change in the C exciton after vanadium doping. Density functional theory calculations show that the band structure is sensitive to the Hubbard U correction for vanadium, and several scenarios are proposed to explain the two photoluminescence peaks around the A exciton energy region. This work provides the first broadband optical characterization of these 2D dilute magnetic semiconductors, shedding light on the novel and tunable electronic features of V‐doped WS2 monolayers.

Heavily vanadium-doped LiFePO4 olivine as electrode material for Li-ion aqueous rechargeable batteries

Since LiFePO4 batteries play a major role in the transition to safe, more affordable and sustainable energy production, numerous strategies have been applied to modify LFP cathode, with the aim of improving its electrochemistry. In this contribution, a highly vanadium-doped LiFe0.9V0.1PO4/C composite (LFP/C-10V) is synthesized using the glycine combustion method and characterized by x-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetry Differential Thermal Analysis (TGDTA) and Cyclic Voltammetry (CV). It is shown that 10wt.% of vanadium can substitute Fe positions, thus decreasing unit cell volume, which is followed by generation of Li3V2PO4 traces, as detected by CV. High vanadium doping does not change the carbon content in the composite (≈13 wt%) but improves its electronic conductivity and electrochemical performance in both aqueous and organic electrolytes. The reversibility and current response are increasing following the trend: LFP/C, LFP/C -3mol%V, LFP/C - 5 mol % and LFP/C-10 mol %. The best specific capacity is obtained for the most highly doped olivine, which exhibits a reversible process at 1 mV s−1 in an aqueous electrolyte, thus showing a peak-to-peak distance of 56 mV. The high capacity of LFPC-10V is measured in both LiNO3 and NaNO3 electrolytes amounting to around 100 mAh g−1 at 20 mV s−1. Still, the material is only stable in LiNO3 electrolyte, making it more suitable for Li than Na-ion aqueous rechargeable batteries.

NASICON-structure Na3+xMnVxTi1-x(PO4)3/C cathode for sodium-ion battery with excellent cycling performance and high specific capacity

The recently discovered Na3MnTi(PO4)3 cathode material has an extremely high theoretical capacity, but its poor cycling performance makes it challenging to apply. In this work, a series of NASICON-type Na3+xMnVxTi1-x(PO4)3/C (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1) cathode materials were prepared by sol-gel method for sodium-ion batteries. X-ray diffraction (XRD) indicates that vanadium doping has increased the cell spacing within the material and the cell volume. From the results of X-ray photoelectron spectroscopy (XPS) and Energy dispersive X-ray spectroscopy (EDS) mapping images, it is shown that vanadium has been successfully doped into the material. Among them, the Na3·3MnV0·3Ti0·7(PO4)3/C delivers an outstanding specific capacity (121.7 mAh g−1 at 0.1C, C = 135 mA g−1) and Na3·4MnV0·4Ti0·6(PO4)3/C shows an excellent capacity retention (80.88 % after 1500 cycles at 1C). Notably, the coulombic efficiency of both materials during cycling is close to 100 %, indicating that these materials have great practical application value.

Noticeable influence of V-dopant on optoelectronic properties of ZnO films prepared by SILAR technique

Wide bandgap semiconductors such as Zinc Oxide (ZnO) have earned much attention on account of its interesting optical and electrical properties. Also, doping ZnO with suitable transition elements enables to tune its properties, making it suitable for applications like transparent conducting oxides and LEDs. To this aim, Vanadium-doped ZnO (V:ZnO) thin films are fabricated using the SILAR method and studied the structural, optical, vibrational, photophysical and electrical properties. Introducing vanadium creates lattice relaxation in the ZnO wurtzite structure, influencing its electronic band structure. The X-ray diffraction (XRD) analyses have verified the structural integrity of the vanadium-doped zinc oxide (V:ZnO) films, revealing their polycrystalline composition. The Raman spectroscopy shows the reduced phonon line widths due to the improved crystallite quality with the presence of vanadium. Furthermore, it has been noted that optical characteristics such as the bandgap and refractive index are sensitive to vanadium doping as a consequence of modified electronic structures. Hall-effect experiments have shown that undoped ZnO films possess a mobility of 1.31 cm2/Vs and a charge carrier density of 5.58 × 1013 cm−3. It has been observed that doping with V markedly influences these parameters of ZnO films. Then, the time-resolved photoluminescence measurements reveal the increased carrier lifetimes, suggesting the introduction of dopants mitigates carrier-phonon interactions. Such interactions need to be minimized to prevent the dissipation of carrier energy. In essence, the reported work demonstrates the potential of V:ZnO for optoelectronic applications.

Arguments on the estimation of V ion distribution at various sites contributing to saturation magnetization in Mn–Zn ferrites

Mn0.6Zn0.4VxFe2-xO4 (x = 0.00–0.10, in steps of 0.02) are synthesized by the solid-state reaction method with a sintering temperature of 1250 °C. X-ray diffraction of the samples confirms the formation of the spinel structure. The grain size is found to increase in morphological investigation of the surface of the samples. The distribution of cations upon vanadium doping in manganese zinc ferrites has not been widely studied before. This study highlights our attempt to formalize a cation distribution to explain our experimental results. Vanadium ions occupying B-sites in their trivalent form may explain the decreasing trend observed in the cell parameters and saturation magnetization, MS values. To support this, theoretical cell parameters and theoretical magnetic moments have been calculated.

Tuning structure, stability and magnetism in vanadium doped zinc sulfide for spintronic applications: Insights from first-principles and Monte Carlo approaches

This work utilizes a multi-scale computational approach combining first-principles density functional theory (DFT) and Monte Carlo statistical simulations to provide fundamental insights into the impacts of vanadium (V) doping on the structural, electronic, magnetic, and thermodynamic properties of wurtzite zinc sulfide (ZnS). 2 × 2 × 2 ZnS supercells with controlled V doping concentrations from 12.5%–25% substituting zinc sites were constructed. The introduction of V dopants induces systematic expansions in lattice parameters and cell volume, attributed to the larger ionic radius of V2+ than Zn2+, while the average compressibility shows minimal variation. However, V incorporation is found to soften ZnS by over 15% at higher dopant contents, increasing compliance and anisotropy. Stable ferromagnetic spin couplings emerge, mediated by host carriers without precipitating V secondary phases. The band structure develops half-metallic electronic properties with the lifting of spin degeneracy and preferential spin-up band metallicity induced by V-3d and S-3p hybridization effects. This results in 100% spin polarization at the Fermi level. Monte Carlo simulations based on a tight-binding Hamiltonian constructed from maximally localized Wannier functions to accurately calculate the exchange interactions between V spins successfully reproduce the magnetic phase transition behavior. The results confirm high Curie temperatures exceeding 300 K at 25% V, attributable to the significant strengthening of short-range ferromagnetic couplings over antiferromagnetic interactions. The integrated computational approach provides fundamental insights into the microscopic origin of carrier-mediated ferromagnetism in V-doped wurtzite ZnS dilute magnetic semiconductors. The systematic first-principles calculations and statistical mechanics modeling establish clear structure–property relationships linking V doping configurations and concentrations to tuned mechanical response, enhanced stability, electronic structure modifications, spin polarization, and magnetic ordering temperatures in ZnS. The results present design pathways and predictive capabilities to guide experimental efforts toward emerging high-performance magnetic materials for spintronic technologies.

Influence of vanadium and dysprosium co-doping on phase stability, microstructure, and electrical properties of Bi2O3

Herein, we report the synthesis of Dy–V co-doped Bi2O3 ceramics using the solid–state processing technique under atmospheric conditions. The X-ray diffraction (XRD) patterns demonstrate the stability of the cubic fluorite δ-Bi2O3 in the V-rich ceramics. However, in Dy-rich ceramics, a mixture of phases, including α and δ, gradually diminishes with increased mutual dopant concentrations, suggesting a transition to the single fcc δ-phase with Fm-3 m space group. According to the Rietveld analysis and electron density representation, it is evident that there are no impure peaks present in α-Bi2O3, which highlights the clear transition to the δ-phase polymorphs. The DTA curves for samples M4 and M7 display a distinct endothermic peak at temperatures around 724.5 and 744.5 °C, indicating a phase transition from the monoclinic α-phase to the cubic δ-phase. These peaks are also attributed to an order-disorder transition (ODT). The FESEM micrographs consistently revealed the existence of irregular and aggregated grains, with an average grain size ranging from 0.80 to 5.57 μm. The level of aggregation became more apparent with the escalation of Dy3+ doping, as opposed to the 5–20 wt% V loading. Moreover, the as-sintered pellets M2 demonstrated the absence of any pore formation compared to other samples, confirming a remarkably high degree of densification. As a result, the as-sintered pellets have a low level of void space, with an apparent porosity of no more than 2.5%. Based on the conductivity measurements and electrochemical impedance spectroscopy (EIS), Bi0.85V0.10Dy0.05O1.5 exhibits the highest electrical conductivity of 0.965 (Ω cm)−1 and an optimal activation energy of 0.537 eV at 627 °C compared to other prepared compositions. This remarkable performance is attributed to the high polarizability and mixed valence cations, especially in V5+-rich ceramics, compared to the Dy3+-rich compositions with a reduced conductivity of 0.010 to 0.097 (Ω cm)−1. The Nyquist plots indicate that impedance decreases with vanadium doping increases until it reaches Bi0.85V0.10Dy0.05O1.5. Higher Dy3+ content increases impedance, leading to lower cell performance. The typical composition can be a solid electrolyte in SOFCs operating at moderate temperatures.