Synthesis and electrochemical characterization of LiCoxMn1−xPO4/C nanocomposites

LiCo_xMn_1−xPO₄/C nanocomposites (0 ≤ x ≤ 1.0) were prepared by a combination of spray pyrolysis at 300 °C and wet ball-milling followed by heat treatment at 500 °C for 4 h in 3% H₂ + N₂ atmosphere. X-ray diffraction analysis indicated that all samples had the single phase olivine structures indexed by orthorhombic Pmna. The lattice parameters linearly decreased with increasing cobalt content, which confirmed the existence of solid solutions. It was clearly seen from the scanning electron microscopy observation that the LiCo_xMn_1−xPO₄/C samples were agglomerates with approximately 100 nm primary particles. The LiCo_xMn_1−xPO₄/C nanocomposites were used as cathode materials for lithium batteries, and electrochemical performance was comparatively investigated with cyclic voltammetry and galvanostatic charge–discharge test using the Li?1 M LiPF₆ in EC:DMC = 1:1?LiCo_xMn_1−xPO₄/C cells at room temperature. The cells at 0.05 C charge–discharge rate delivered first discharge capacities of 165 mAh g⁻¹ (96% of theoretical capacity) at x = 0, 136 mAh g⁻¹ at x = 0.2, 132 mAh g⁻¹ at x = 0.5, 125 mAh g⁻¹ at x = 0.8 and 132 mAh g⁻¹ (79% of theoretical capacity) at x = 1.0, respectively. While the first discharge capacity increased with the cobalt content at high charge–discharge rates more than 0.5 C due to higher electronic conductivity of LiCoPO₄ in comparison with LiMnPO₄, the cycleability of cell became worse with increasing the amount of cobalt. The existence of Mn²⁺ seemed to enhance the cycleability of LiCo_xMn_1−xPO₄/C nanocomposite cathode.     

Optimized electrochemical performance of LiMn0.9Fe0.1−xMgxPO4/C for lithium ion batteries

A series of LiMn_0.9Fe_0.1−xMg_xPO₄/C (x = 0, 0.01, 0.02, 0.05) was synthesized by a solid state reaction, and the effect of synthesis temperature and Fe/Mg ratio on the electrochemical performance of the obtained materials was investigated by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and electrochemical measurements. The electrochemical performance of the Fe and Mg co-substituted LiMnPO₄ was obviously improved with increasing synthesis temperature from 650 to 800 °C, but further increase led to an abrupt capacity loss due to the impurity formation. The Fe and Mg co-substitution could remarkably enhance the electrochemical activity of LiMnPO₄ compared with the Fe substitution only, but too high level of Mg doping would worsen the rate capability. The LiMn_0.9Fe_0.09Mg_0.01PO₄/C synthesized at 800 °C demonstrated the optimum electrochemical performance with a high capacity and an excellent rate capability. Even discharged at the rate of 10 C, a capacity of 60 mAh g⁻¹ was still observed.     

Synthesis of Ti1−xSnxO2 nanosized photocatalysts in reverse microemulsions

The preparation of Ti_1−xSn_xO₂ nanocrystalline photocatalysts in reverse microemulsions is reported in this work. The obtained materials have been characterised by total reflection X-ray fluorescence (TXRF), X-ray diffraction (XRD) and Raman and UV–vis spectroscopies. Very good accordance between calculated and obtained compositions is observed. Undoped TiO₂ prepared in this way crystallises in the anatase phase. Tin-doped anatase is formed with x < 0.05, while both anatase and rutile phases crystallise when x ≥ 0.05. When both phases coexist, a preferential doping of rutile seems to occur. When x = 0.10, a multiphase mixture containing TiO₂(anatase), TiO₂(rutile) and SnO₂ was formed. No significant modification of the band gap is found in any case. The photocatalytic activity of the obtained catalysts is compared employing the trichloroethylene photocatalytic degradation as a test reaction. The beneficial effect of Sn⁴⁺ in the activity of TiO₂ appears to be related to the formation of anatase–rutile mixtures, leading to the highest specific photocatalytic activity in the sample of composition Ti_0.93Sn_0.07O₂, with anatase:rutile ratio close to 3.     

Synthesis, structural analysis and electrochemical performance of low-copper content La2Ni1−xCuxO4+δ materials as new cathodes for solid oxide fuel cells

In order to enhance the electrochemical performance of solid oxide fuel cells (SOFCs), La₂Ni_1−xCuO_4+δ (x = 0, 0.01, 0.02, 0.05 and 0.1) doped with copper in percentages, varying between 1% and 10%, were prepared following the modified Pechini method. The microstructure and morphology of the samples were analyzed by XRD and SEM. The electrochemical performance was followed by impedance spectroscopy. La₂Ni_0.99Cu_0.01O_4+δ samples showed good electrochemical and physicochemical properties with respect to the undoped material and is potentially a promising cathode. Indeed, doping with such small amounts of copper (1%) into the nickel site led to the formation of pure phases and stabilized the material before and after use at high temperature under air. In contrast, doping with higher amounts of copper (2%, 5% and 10%) led, after heating at 1000 °C for 48 h, to the formation of another phase resulting from the diffusion of copper into the YSZ electrolyte, limiting the interest to these materials as SOFC cathodes.     

Evolution of microstructure,optical, and magnetic properties in multiferroic CuFe1-xSnxO2 (x = 0–0.05)

Evolution of the microstructure, optical, and magnetic properties have been investigated systematically in multiferroic CuFe_1-xSn_xO₂ (x?=?0–0.05) ceramics. Substitution of Sn⁴⁺ for Fe³⁺ results in expansion of CuFeO₂ lattice, and reduces the density of the material, but the metal oxidation states are unchanged. Observation of the optical properties shows that the value of the direct optical band gap (E_g) decreases with increasing Sn doping level, and that the CuFe_1-xSn_xO₂ (x?=?0–0.04) series with values >?3.1?eV. Magnetic susceptibility measurements show that Sn⁴⁺ doping decreases the Curie-Weiss temperature, i.e. weakens the strength of the antiferromagnetic interaction between high-spin Fe³⁺ ions, but does not affect the stability of the antiferromagnetic phase, and all samples undergo successive magnetic transitions at about T_N1 =?15?K and T_N2 =?11?K. However, magnetization curves show that changes occur in the magnetic interactions and both ferromagnetism and antiferromagnetism co-exist in the Sn⁴⁺-doped samples. The maximum value of the saturation magnetization of 1.8?emu·g^?1 was observed for the x?=?0.03 sample in a 2.5?kOe field. The changes in the magnetic behavior are closely related to the lattice distortion and charge compensation, which are discussed in detail in this work.     

Properties of Ca1−xHoxMnO3 perovskite-type electrodes

In this work, Ca_1−xHo_xMnO₃ (x = 0, 0.1 and 0.2) perovskite oxide pelleted electrodes were prepared from the respective powders obtained by the citrate route method at 1173 K.The electrodes exhibit particle size that decreases with the holmium content in the oxide. All the samples reveal semiconductor behaviour and the presence of holmium induces a marked decrease in the electrical resistivity. The results can be well attributed to the changes in the Mn⁴⁺/Mn³⁺ ratio. Electrodes were characterized by cyclic voltammetry and chronopotentiometry. Cyclic voltammetric studies indicate a similar behaviour of the electrodes, irrespective of their composition. Two pairs of peaks were identified and associated, one to the Mn⁴⁺/Mn³⁺ redox couple and the other to the Mn⁷⁺/Mn⁴⁺ and Mn⁶⁺/Mn⁴⁺ redox couples. The voltammetric data provide evidence that the electrodes roughness factor increases with the introduction of Ho-ions in the oxide structure, what is consistent with the crystallite size obtained by X-ray diffraction (XRD) and the morphology observed by scanning electron microscopy (SEM). The Ho-substituted electrodes present higher current density when compared with CaMnO₃ electrodes what can be attributed both to higher electrical conductivity and smaller particle size. The chronopotentiometric studies have shown that the discharge occurs by different mechanisms for the oxide electrodes with and without Ho.     

La(1−x)SrxCo1−yFeyO3 perovskites prepared by sol–gel method: Characterization and relationships with catalytic properties for total oxidation of toluene

La_(1−x)Sr_xCo_(1−y)Fe_yO₃ samples have been prepared by sol–gel method using EDTA and citric acid as complexing agents. For the first time, Raman mappings were achieved on this type of samples especially to look for traces of Co₃O₄ that can be present as additional phase and not detect by XRD. The prepared samples were pure perovskites with good structural homogeneity. All these perovskites were very active for total oxidation of toluene above 200 °C. The ageing procedure used indicated good thermal stability of the samples. A strong improvement of catalytic properties was obtained substituting 30% of La³⁺ by Sr²⁺ cations and a slight additional improvement was observed substituting 20% of cobalt by iron. Hence, the optimized composition was La_0.7Sr_0.3Co_0.8Fe_0.2O₃. The samples were also characterized by BET measurements, SEM and XRD techniques. Iron oxidation states were determined by Mössbauer spectroscopy. Cobalt oxidation states and the amount of O⁻ electrophilic species were analyzed from XPS achieved after treatment without re-exposition to ambient air. Textural characterization revealed a strong increase in the specific surface area and a complete change of the shape of primary particles substituting La³⁺ by Sr²⁺. The strong lowering of the temperature at conversion 20% for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples can be explained by these changes. X photoelectron spectra obtained with our procedure evidenced very high amount of O⁻ electrophilic species for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples. These species able to activate hydrocarbons could be the active sites. The partial substitution of cobalt by iron has only a limited effect on the textural properties and the amount of O⁻ species. However, Raman spectroscopy revealed a strong dynamic structural distortion by Jahn–Teller effect and Mössbauer spectroscopy evidenced the presence of Fe⁴⁺ cations in the iron containing samples. These structural modifications could improve the reactivity of the active sites explaining the better specific activity rate of the La_0.7Sr_0.3Co_0.8Fe_0.2O₃ sample. Finally, an additional improvement of catalytic properties was obtained by the addition of 5% of cobalt cations in the solution of preparation. As evidenced by Raman mappings and TEM images, this method of preparation allowed to well-dispersed small Co₃O₄ particles that are very efficient for total oxidation of toluene with good thermal stability contrary to bulk Co₃O₄.     

Aluminothermal synthesis and characterization of Li3V2−xAlx(PO4)3 cathode materials for lithium ion batteries

Monoclinic Li₃V_2−xAl_x(PO₄)₃ with different Al³⁺ doping contents (x = 0, 0.05, 0.08, 0.10 and 0.12) have been prepared by a facile aluminothermal reaction. Aluminum nanoparticles have been used as source for Al³⁺ and nucleus for Li₃V_2−xAl_x(PO₄)₃ nucleation as well as reducing agent in the aluminothermal strategy. The products were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and electrochemical methods. The XRD results show that the as-obtained Li₃V_2−xAl_x(PO₄)₃ has a phase-pure monoclinic structure, irrespective of the Al³⁺ doping concentration. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) results reveal that the charge-transfer resistance of the Li₃V₂(PO₄)₃ is reduced and the reversibility is enhanced after V³⁺ substituted by Al³⁺. In addition, The Li₃V_2−xAl_x(PO₄)₃ phases exhibit better cycling stability than the pristine Li₃V₂(PO₄)₃.     

High-performance Li4Ti5−xVxO12 (0 ≤ x ≤ 0.3) as an anode material for secondary lithium-ion battery

Powders of spinel Li₄Ti_5−xV_xO₁₂ (0 ≤ x ≤ 0.3) were successfully synthesized by solid-state method. The structure and properties of Li₄Ti_5−xV_xO₁₂ (0 ≤ x ≤ 0.3) were examined by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electronic microscope (SEM), galvanostatic charge–discharge test and cyclic voltammetry (CV). XRD shows that the V⁵⁺ can partially replace Ti⁴⁺ and Li⁺ in the spinel and the doping V⁵⁺ ion does almost not affect the lattice parameter of Li₄Ti₅O₁₂. Raman spectra indicate that the Raman bands corresponding to the Li–O and Ti–O vibrations have a blue shift due to the doping vanadium ions, respectively. SEM exhibits that Li₄Ti_5−xV_xO₁₂ (0.05 ≤ x ≤ 0.25) samples have a relative uniform morphology with narrow size distribution. Charge–discharge test reveals that Li₄Ti_4.95V_0.05O₁₂ has the highest initial discharge capacity and cycling performance among all samples cycled between 1.0 and 2.0 V; Li₄Ti_4.9V_0.1O₁₂ has the highest initial discharge capacity and cycling performance among all samples cycled between 0.0 and 2.0 V or between 0.5 and 2.0 V. This excellent cycling capability is mainly due to the doping vanadium. CV reveals that electrolyte starts to decompose irreversibly below 1.0 V, and SEI film of Li₄Ti₅O₁₂ was formed at 0.7 V in the first discharge process; the Li₄Ti_4.9V_0.1O₁₂ sample has a good reversibility and its structure is very advantageous for the transportation of lithium-ions.     

Layered NdBaCo2−xNixO5+δ perovskite oxides as cathodes for intermediate temperature solid oxide fuel cells

The effect of Ni substitution on the crystal chemistry, thermal and electrochemical properties, and catalytic activity for oxygen reduction reaction of the layered NdBaCo_2−xNi_xO_5+δ perovskite oxides has been investigated for 0 ≤ x ≤ 0.6. The oxygen content (5 + δ) and oxidation state of the (Co, Ni) ions in the air-synthesized NdBaCo_2−xNi_xO_5+δ samples decrease with increasing Ni content, accompanied by a structural transition from tetragonal (0 ≤ x ≤ 0.4) to orthorhombic (x = 0.6). Similarly, the thermal expansion coefficient (TEC) and electrical conductivity also decrease with increasing Ni content. The x = 0.2 and 0.4 samples exhibit slightly improved performance as cathodes in single cell solid oxide fuel cell (SOFC) compared to the x = 0 sample, which is in accordance with the ac-impedance data. Among the samples studied, the x = 0.4 sample exhibits a combination of low thermal expansion and high catalytic activity for the oxygen reduction reaction in SOFC.     

Decolorization of methylene blue by heterogeneous Fenton reaction using Fe3−xTixO4 (0 ≤ x ≤ 0.78) at neutral pH values

In this work, a series of Fe_3−xTi_xO₄ (0 ≤ x ≤ 0.78) was synthesized using a new soft chemical method. The synthetic Fe_3−xTi_xO₄ were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Mössbauer spectroscopy, thermogravimetric and differential scanning calorimetry (TG–DSC) analyses. The results showed that they were spinel structures and Ti was introduced into their structures.Then, decolorization of methylene blue (MB) by Fe_3−xTi_xO₄ in the presence of H₂O₂ at neutral pH values was studied using UV–vis spectra, dissolved organic carbon (DOC) and element C analyses. Furthermore, the degradation products remained in reaction solution after the decolorization were identified using ionic chromatography (IC), ¹³C nuclear magnetic resonance spectra (NMR), liquid chromatography and mass spectrometry (LC–MS). Although small amounts of MB were mineralized, the aromatic rings in MB were destroyed completely after the decolorization. Decolorization of MB by Fe_3−xTi_xO₄ in the presence of H₂O₂ was promoted remarkably with the increase of Ti content in Fe_3−xTi_xO₄ due to the enhancement of both adsorption and degradation of MB on Fe_3−xTi_xO₄.     

Structure and magnetic properties of Fe1−xCox nanowires in self-assembled arrays

Fe_1−xCo_x nanowires in self-assembled arrays with varying compositions were produced by the template-assisted pulsed electrochemical deposition method. The structural and magnetic properties of the arrays were investigated using several experimental techniques. TEM analyses indicated that the nanowires were regular, uniform, 8 μm in length and 50 nm in diameter. The results of X-ray diffraction indicated that the body-centered-cubic (bcc) (α), face-centered-cubic (fcc) (γ), and hexagonal-close-packed (hcp) () Fe–Co phases appeared in different compositions. Magnetic measurements showed that the coercivity and squareness of the hysteresis loops of the Fe_1−xCo_x changed with their compositions, which may be attributable to shape anisotropy. The room temperature ⁵⁷Fe Mössbauer spectra of the arrays of the Fe_1−xCo_x nanowires revealed strong shape anisotropy.     

Preparation, structure and electrical conductivity of pyrochlore-type Gd1−xEu2xSm1−xZr2O7 ceramics with a constant lattice parameter

A novel series of Gd_1−xEu_2xSm_1−xZr₂O₇ (x = 0, 1/3, 1/2, 2/3, 1) ceramics with a constant lattice parameter are prepared by solid-state reaction, and are then evaluated as possible solid electrolytes. The microstructure and electrical properties of Gd_1−xEu_2xSm_1−xZr₂O₇ ceramics have been investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and complex impedance analysis. Gd_1−xEu_2xSm_1−xZr₂O₇ ceramics exhibit a single phase of pyrochlore-type structure. The total conductivity of Gd_1−xEu_2xSm_1−xZr₂O₇ ceramics obeys the Arrhenius relation, and gradually increases with increasing temperature from 723 to 1173 K. At 973–1173 K, the composition has little effect on electrical conductivity of Gd_1−xEu_2xSm_1−xZr₂O₇ ceramics. Gd_1−xEu_2xSm_1−xZr₂O₇ ceramics are oxide-ion conductors in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The maximum total conductivity of Gd_1−xEu_2xSm_1−xZr₂O₇ ceramics is about 1.01 × 10⁻² S cm⁻¹ at 1173 K in air.     

Electrochemical and ex situ XRD investigations on (1−x)LiNiO2·xLi2TiO3 (0.05≤x≤0.5)

An attempt to understand the unusual electrochemical behaviors in (1−x)LiNiO₂·xLi₂TiO₃ (0.05≤x≤0.5), an excess initial charge capacity exceeding the oxidation of transitional metal to +4 accompanying the appearance of an irreversible initial charge plateau when x reached 0.075, was performed. The decreased charge-discharge polarization after charging to 4.6 and 4.8 V and increased columbic reversibility after charging to 4.6 V typically for x=0.1 and 0.2, in contrast to charging to 4.4 V, suggested that the excess initial charge capacity possibly did not come mainly from electrolyte decomposition; while ex situ XRD results in the sample with x=0.2 confirmed that Li⁺ were really extracted at the stage of the charge plateau, ruling out the possibility that electrolyte decomposition mainly accounted for the unusual electrochemical behaviors. It was inferred that the species responsible for charge compensation for the excess charge capacity must be oxygen ions in these materials, considering that Ni⁴⁺ and Ti⁴⁺ are generally impossible to be oxidized to a higher valence. Various electrochemical cycling experiments demonstrated that the sample for x=0.05 with high resistant ability to high voltage and temperature is very promising cathode material in view of observed capacity and cycleability from a viewpoint of application.     

Structure,magnetic and electrical transport properties of the perovskites Sm1−xCaxFe1−xMnxO3

The structure of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.0 ≤ x ≤ 1.0) compounds was investigated. The lattice parameters increase with coupled substitution Sm³⁺ by Ca²⁺ and Mn⁴⁺ for Fe³⁺. The variation of parameter, c, is larger than that of a and b, respectivly. The detailed analysis of magnetic properties of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.1 ≤ x ≤ 0.9) shows that local magnetic interaction between Fe³⁺ and Fe³⁺ and Mn⁴⁺ and Mn⁴⁺ at below magnetic transition temperature is antiferromagnetic. Above magnetic transition temperature the presence of large magnetic cluster is proposed and the sizes of magnetic clusters decrease with Mn⁴⁺. The electrical transport behaviors related with small polaron hopping and variable range hopping models.     

Formation Behavior and High Electrical Conductivity of Metastable Lithium Iron Silicate Crystals in Rapid Quenching of Li2O–Fe2O3–SiO2 Melts

The formation behavior of spinel‐type LiFeSiO₄ crystals in the quenching of melts in the Li₂O–Fe₂O₃–SiO₂ system was examined. It was found that high quenching rates of 10³ ~ 10⁶ K/min are favorable for the formation of LiFeSiO₄ crystals. The rapid quenched samples showed high electrical conductivities of the order of 10^?2–10^?4 S/cm at room temperature and low activation energy for conduction of 0.1–0.2 eV. Both valences of Fe²⁺ and Fe³⁺ were present in the melt‐quenched samples, and rapid‐quenched samples showed ferrimagnetism. It is proposed that the chemical composition of LiFeSiO₄ formed in the rapid quenching of melts would be spinel‐type Li_1 + xFe³⁺_1 ? xFe²⁺_xSiO₄. Because the Li_1 + xFe³⁺_1 ? xFe²⁺_xSiO₄ crystalline phases are metastable, the rapid quenching technique is necessary for their synthesis. The effects of quenching rate and composition on the formation of spinel‐type LiFeSiO₄ and on the electrical conductivity of quenched samples were discussed.     

Enhanced transport properties of Sn-substituted proton-conducting BaZr0.8Sc0.2O3–δ ceramic materials

High-temperature proton conductors based on acceptor-doped barium zirconate exhibit excellent chemical stability in atmospheres containing CO₂ or H₂O. However, due to their refractory nature, these conductors have a low grain growth rate, which negatively affects the overall electrical conductivity. A possible strategy for increasing the ionic conductivity of zirconates lies in the partial substitution of Zr-ions with other isovalent dopants. In this work, we carried out systematic studies of the crystal structure, microstructure, hydration capacity, transport, and thermal properties of BaZr_0.8–xSn_xSc_0.2O_3–δ (x = 0, 0.1, and 0.2). According to X-ray powder diffraction and scanning electron microscopy data, all studied ceramic samples have a cubic perovskite structure, whose average grain size decreases with tin doping. It is found that the composition with x = 0.1 exhibits the highest values in terms of total, ionic, grain, and grain-boundary conductivities. The complex analysis of the obtained data shows that a low-level substitution of Zr⁴⁺- with Sn⁴⁺-ions is a competent approach for designing new proton-conducting electrolytes attractive for high-temperature applications.     

Evolution of the local structure and electrochemical properties of spinel LiNixMn2−xO4 (0 ≤ x ≤ 0.5)

A series of Ni substituted spinel LiNi_xMn_2−xO₄ (0 ≤ x ≤ 0.5) have been synthesized to study the evolution of the local structure and their electrochemical properties. X-ray diffraction showed a few Ni cations moved to the 8a sites in heavily substituted LiNi_xMn_2−xO₄ (x ≥ 0.3). X-ray photoelectron spectroscopy confirmed Ni²⁺ cations were partially oxidized to Ni³⁺. The local structures of LiNi_xMn_2−xO₄ were studied by analyzing the and A_1g Raman bands. The most compact [Mn(Ni)O₆] octahedron with the highest bond energy of Mn(Ni)O was found for LiNi_0.2Mn_1.8O₄, which showed a Mn(Ni)O average bond length of 1.790 Å, and a force constant of 2.966 N cm⁻¹. Electrolyte decomposition during the electrochemical charging processes increased with Ni substitution. The discharge capacities at the 4.1 and 4.7 V plateaus obeyed the linear relationships with respect to the Ni substitution with the slopes of −1.9 and +1.9, which were smaller than the theoretical values of −2 and +2, respectively. The smaller slopes could be attributed to the electrochemical hysteresis and the presence of Ni³⁺ in the materials.     

Influence of manganese substitution into the A-site of perovskite type Ca1−xMnxTiO3 ceramic

Ca_1−xMn_xTiO₃ (x = 0–1.0) perovskite ceramics were prepared by conventional solid state reaction. XRD was used to confirm the microcrystalline nature of the Ca_1−xMn_xTiO₃ crystals. For the x = 0 composition, the XRD patterns were those of a single orthorhombic perovskite while for x = 0.2–0.8, the XRD spectra were those of two orthorhombic perovskite phases: CaTiO₃ and MnTiO₃. For x = 1, XRD pattern was that of the MnTiO₃ phase only. The morphology and particle size of the grains of the different composition were observed using SEM. The size of the particles increased from 0.2 μm to 2–3 μm as x increased from 0 to 0.6. The room temperature dielectric constant at the frequency of 110 kHz for the x = 0.2 and x = 1.0 ceramics were ∼3.41 × 10⁴ and ∼4.99 × 10³, respectively. The ESR linewidth of samples increased with increasing manganese content due to the formation of magnetic cluster. Our ESR studies indicate that the manganese ions are in the Mn⁴⁺ state.     

Structural,Raman, and Dielectric Studies on Multiferroic Mn‐doped Bi1−xLaxFeO3 Ceramics

Multiferroic Bi_1?xLa_xFeO₃ [BLFO (x)] ceramics with x = 0.10–0.50 and Mn‐doped BLFO (x = 0.30) ceramics with different doping contents (0.1–1.0 mol%) were prepared by solid‐state reaction method. They were crystallized in a perovskite phase with rhombohedral symmetry. In the BLFO (x) system, a composition (x)‐driven structural transformation (R3c→C222) was observed at x = 0.30. The formation of Bi₂Fe₄O₉ impure phase was effectively suppressed with increasing the x value, and the rhombohedral distortion in the BLFO ceramics was decreased, leading to some Raman active modes disappeared. A significant red frequency shift (~13 cm^?1) of the Raman mode of 232 cm^?1 in the BLFO ceramics was observed, which strongly perceived a significant destabilization in the octahedral oxygen chains, and in turn affected the local FeO₆ octahedral environment. In the Mn‐doped BLFO (x = 0.30) ceramics, the intensity of the Raman mode near 628 cm^?1 was increased with increasing the Mn‐doping content, which was resulted from an enhanced local Jahn–Teller distortions of the (Mn,Fe)O₆ octahedra. Electron microscopy images revealed some changes in the ceramic grain sizes and their morphologies in the Mn‐doped samples at different contents. Wedge‐shaped 71° ferroelectric domains with domain walls lying on the {110} planes were observed in the BLFO (x = 0.30) ceramics, whereas in the 1.0 mol% Mn‐doped BLFO (x = 0.30) samples, 71° ferroelectric domains exhibited a parallel band‐shaped morphology with average domain width of 95 nm. Dielectric studies revealed that high dielectric loss of the BLFO (x = 0.30) ceramics was drastically reduced from 0.8 to 0.01 (measured @ 10⁴ Hz) via 1.0 mol% Mn‐doping. The underlying mechanisms can be understood by a charge disproportion between the Mn⁴⁺ and Fe²⁺ in the Mn‐doped samples, where a reaction of Mn⁴⁺ + Fe²⁺→Mn³⁺ + Fe³⁺ is taken place, resulting in the reduction in the oxygen vacancies and a suppression of the electron hopping from Fe³⁺ to Fe²⁺ ions effectively.