Search Results (64)

Lead-free [(Ba_0.85Ca_0.15)_1−1.5xNd_x][(Zr_0.1Ti_0.9)_0.995Mn_0.005]O₃ (x mol% Nd/Mn BCZT, x = 0.05, 0.1, 0.5, 1 mol%) ceramics were prepared by the traditional solid-state reaction method, in which the synergistic effects of sintering temperature and Nd/Mn co-doping on the phase structure, microstructural evolution, and electrical properties were systematically investigated. All ceramics exhibit a pure perovskite structure, with the tetragonal (P4mm) phase dominating at room temperature as confirmed by the X-ray diffraction Rietveld refinement. The sintering temperature (1475–1520 °C) is found to be the primary factor governing densification and grain growth, with the relative density peaking at 91.7% for the x = 0.5 mol% sample sintered at 1505 °C. Within this optimized processing window, increasing the Nd content induces a gradual migration of the Curie temperature (T_C) toward lower temperatures, accompanied by enhanced relaxor behavior. A highlight of this work is the strategic balance between piezoelectric activity and mechanical quality factor through a “donor–acceptor” co-doping mechanism. Specifically, for the x = 0.5 mol% ceramics, an exceptionally high mechanical quality factor (Q_m = 424.5) is achieved for samples sintered at 1490 °C, which is proposed to be associated with the temperature-modulated formation of ${Mn}_{Ti}^{″}-V_O^{••}$ defect dipoles, while a peak inverse piezoelectric coefficient $d_{33}^{*}$ of 685.1 pm/V is maintained at a sintering temperature of 1520 °C. Full article

Pr³⁺-activated phosphors are promising for non-contact optical thermometry under blue-light excitation. In tantalate hosts, Pr³⁺-Ta⁵⁺ intervalence charge transfer (IVCT) states may introduce thermally activated nonradiative pathways involving the ³P₀ and ¹D₂ levels, thus affecting their thermal quenching behavior and thermometric performance. However, the concentration- and temperature-dependent luminescence of CaTa₂O₆:Pr³⁺ remains unexplored. In this study, CaTa₂O₆:Pr³⁺ phosphors were synthesized via the solid-state reaction method, and a phosphor-in-glass (PiG) composite was fabricated by co-sintering the mixture of the phosphor and the precursor glass (PG) powder. The structural characteristics and the luminescence properties of CaTa₂O₆:Pr³⁺ phosphors under 450 nm excitation were investigated. The IVCT band was confirmed in the excitation spectrum. Optimal Pr³⁺ concentrations were 2 mol% for ³P_J and 0.7 mol% for ¹D₂ emissions. With Pr³⁺/Zr⁴⁺ or Pr³⁺/Sn⁴⁺ co-doping, the emission intensity was enhanced by 1.34 and 1.31 times, respectively. The PiG exhibited similar spectral profiles. An FIR mode based on ³P₁→³H₅/³P₀→³F₂ transitions achieved maximum relative sensitivities of 1.09% K⁻¹ for the phosphor and 1.18% K⁻¹ for the PiG at 298 K. These findings suggest that CaTa₂O₆:Pr³⁺-based materials are potential candidates for luminescence thermometry. Full article

Ammonia has emerged as a strategically advantageous hydrogen carrier; however, its efficient decomposition using conventional solid catalysts remains technically challenging from an industrial standpoint, particularly in terms of long-term stability and large-scale implementation. In this study, we propose a strategy for ammonia cracking by utilizing Sn-based molten metal alloys in a bubble column reactor, which provides a sintering-resistant and thermally efficient catalytic platform. Among various candidate transition metals, the Sn-Co alloy exhibited the most superior catalytic performance, demonstrating a significant reduction in the apparent activation energy to 52.6 kJ/mol. To the best of our knowledge, this study provides the first experimental evidence of the catalytic role of molten metals in the ammonia decomposition process. Structural characterization confirmed that the molten alloy maintains its metallic state without the formation of nitrides, verifying the function of the molten metal as an active catalyst rather than a sacrificial reagent. This work offers a new catalytic approach that addresses the requirements for the commercialization of ammonia cracking through improved scalability and chemical durability. Full article

Sulfide-based solid electrolytes are promising for all-solid-state sodium batteries due to their high ionic conductivity and facile processability, but their practical use is limited by moisture sensitivity and poor interfacial stability. To address these issues, Na_3−xPS_4−xM_x (M = F, Cl, Br, I) electrolytes were first synthesized as a preliminary study to evaluate the effect of halogen doping. Chlorine was identified as the most effective dopant and was therefore selected for a systematic investigation of doping concentration. Na_3−xPS_4−xCl_x (x = 0.1–0.3) electrolytes were prepared by solid-state sintering, and the optimum composition was determined to be Na_2.85PS_3.85Cl_0.15, which achieved a high ionic conductivity of 5.5 × 10⁻⁴ S·cm⁻¹ with a reduced activation energy of 33.3 kJ·mol⁻¹. When employed in TiS₂|Na_2.85PS_3.85Cl_0.15|Na₃Sn full cells, the optimized electrolyte enabled high initial capacity, excellent rate capability, and stable long-term cycling. These results highlight the effectiveness of Cl doping concentration control in enhancing both the intrinsic properties of Na₃PS₄-based electrolytes and the overall electrochemical performance of all-solid-state sodium batteries. Full article

The continuous tightening of emission regulations and the escalating costs of palladium (Pd) and rhodium (Rh) have renewed interest in platinum (Pt)-based three-way catalysts (TWCs) as cost-effective alternatives for gasoline aftertreatment. However, despite extensive studies on Pt/CeO₂ and Pt/Ba-based formulations, the cooperative roles of Ba and Ce and, in particular, the fundamental influence of the Ba/Ce ratio on oxygen mobility, NO_x storage behavior, and Pt–support interactions remain poorly understood. In this work, we address this gap by systematically tuning the Ba/Ce molar ratio in a series of Pt–Ba–Ce/Al₂O₃ catalysts prepared from Ba(CH₃COO)₂ and CeO₂ precursors, and evaluating their structure–function relationships in both fresh and hydrothermally aged states. Through comprehensive characterization (N₂ physisorption, XRD, XPS, H₂-TPR, NO_x-TPD, SEM, CO pulse adsorption, and dynamic light-off testing), we establish previously unrecognized correlations between Ba/Ce ratio–dependent structural evolution and TWC performance. The results reveal that the Ba/Ce ratio exerts a decisive control over catalyst textural properties, Pt dispersion, and interfacial Pt–CeO₂ oxygen species. Low Ba/Ce ratios uniquely promote Pt–Ce interfacial oxygen and O₂ spillover—providing a new mechanistic basis for enhanced low-temperature oxidation and reduction reactions—while higher Ba loading selectively drives BaCO₃ formation and boosts NO_x storage capacity. A clear volcano-type dependence of NO_x storage on the Ba/Ce ratio is demonstrated for the first time. Hydrothermal aging at 850 °C induces PtO_x decomposition, BaCO₃–Al₂O₃ solid-state reactions forming inactive BaAl₂O₄, and Pt sintering, collectively suppressing Pt–Ce interactions and reducing TWC activity. Importantly, an optimized Ba/Ce ratio is shown to mitigate these degradation pathways, offering a new design principle for thermally durable Pt-based TWCs. Overall, this study provides new mechanistic insight into Ba–Ce cooperative effects, establishes the Ba/Ce ratio as a critical and previously overlooked parameter governing Pt–support interactions and NO_x storage, and presents a rational strategy for designing cost-effective, hydrothermally robust Pt-based alternatives to Pd/Rh commercial TWCs. Full article

In this study, medium- and high-entropy carbide systems with compositions WC-TiC-TaC-HfC and WC-TiC-TaC-HfC-ZrC were successfully synthesized via a combination of mechanical activation (using high-energy ball milling, HEBM) and spark plasma sintering (SPS) at 1900 °C. Investigation of the SPS consolidation kinetics revealed that both systems undergo single-stage active densification via a solid-state sintering mechanism within the temperature range of 1316–1825 °C. The introduction of ZrC into the five-component system led to a 22% decrease in the maximum shrinkage rate (from 0.9 to 0.7 mm·min⁻¹), which is attributed to the manifestation of a sluggish diffusion effect, characteristic of high-entropy systems. X-ray diffraction analysis of the consolidated samples confirmed the formation of predominantly single-phase high-entropy solid solutions (W-Ti-Ta-Hf)C and (W-Ti-Ta-Hf-Zr)C with a NaCl-type cubic structure (space group Fm-3m) and lattice parameters of 4.4101 Å and 4.4604 Å, respectively. Energy-dispersive X-ray spectroscopy revealed a near-equimolar distribution of metallic components with deviations not exceeding ±1.9 at. %. The addition of ZrC increased the average crystallite size by 84.3% (from 83.6 to 153.1 nm). Both systems achieved comparable relative densities of ~91.75%; however, they exhibited differences in hardness distribution: the four-component system is characterized by a higher average microhardness (1860 HV), while the five-component system exhibits a higher macrohardness HV30 (2008.1). The established correlations between composition, phase formation, microstructure, and properties provide a fundamental basis for the targeted design of high-entropy carbide ceramics with tailored characteristics for high-temperature applications. Full article

A comprehensive study of the structural–phase transformations and hydrogen desorption kinetics in the Mg₅₆Al₄₄ system was conducted using a multistage approach combining thermodynamic modeling CALPHAD, Thermo-Calc 2025a, mechanical synthesis (MS), spark plasma sintering (SPS), and subsequent dispersion treatment. Thermodynamic modeling revealed a stable existence region of the intermetallic compound Mg₁₇Al₁₂, exhibiting Cp-T anomalies at 303 and 351 °C that closely corresponded to the experimental DSC/TGA results. Microstructural analysis showed that varying the ball-to-powder ratio BPR 20:1 and BPR 30:1 determines the defect density, crystallite size 25–45 nm, and lattice strain 1.5–3.0 × 10⁻³, all of which directly influence the hydrogen desorption kinetics. For the samples synthesized at BPR 30:1, the onset temperature of hydrogen release decreased to 180–200 °C while maintaining a hydrogen storage capacity of 4.9 wt.%, accompanied by a reduction in the apparent activation energy of desorption from 92 to 74 kJ·mol⁻¹ according to the Kissinger method. The dispersion stage partially disrupted and redistributed the surface MgO layer, leading to a reduction in its overall contribution and improvement in structural homogeneity, rather than complete oxide removal. The combined MS-SPS-dispersion processing route enabled controlled nanostructure formation, reduced the hydrogen desorption temperature by approximately 100 °C compared to conventional MgH₂-based materials, and significantly enhanced the thermokinetic performance. These findings demonstrate that Mg-Al alloys are promising candidates for solid-state hydrogen storage systems with improved desorption kinetics and reduced activation barriers. Full article

This study investigates the control of the phase-structural state in Ni–45Ti–xCu (x = 5, 7 at.%) shape memory alloys fabricated via a shortened powder metallurgy route: mechanical activation → spark plasma sintering (SPS) → heat treatment. Compact samples were produced from mechanically alloyed powders (650–750 rpm, up to 5 h) and sintered at 900 °C. The structure and microstructure were characterized using X-ray diffraction (to identify B2/B19′/Ni₄Ti₃ phases and assess ordering) and SEM–BSE/EDS (to analyze morphology, porosity, and Ni-rich precipitates). Two post-processing treatments were applied: single-stage annealing (500 °C, 2 h) and a three-stage treatment (900 °C/30 min → water quenching → 300 °C/20 min). Mechanical alloying transformed the initial elemental powder mixture (fcc-Ni, hcp-Ti, fcc-Cu) into a supersaturated fcc-(Ni, Cu, Ti) solid solution with emerging NiTi phases, with a minimum particle size achieved after ~300 min at 750 rpm. SPS compaction yielded a high-density matrix consisting predominantly of the B2 phase. Single-stage annealing preserved B19′ martensite and Ni₄Ti₃ precipitates, particularly in the 5 at.% Cu alloy. In contrast, the three-stage treatment dissolved the Ni₄Ti₃ precipitates, suppressed the formation of B19′ and R phases, and stabilized a highly ordered B2 matrix. Increasing the Cu content from 5 to 7 at.% significantly enhanced the B2 phase fraction, reduced secondary nickel-rich phases, and improved structural homogeneity, evidenced by a continuous neck network and closed porosity. The optimized condition—7 at.% Cu combined with the three-stage annealing—produced a microstructure with >95% B2 phase, <1% Ni₄Ti₃, and ~98% relative density. This forms the prerequisite microstructural state for a narrow transformation hysteresis and high functional cyclic stability. Full article

NASICON-type Li_1+XFe_XTi_2-X(PO₄)₃ (x = 0.1, 0.3, 0.4) solid electrolytes for all-solid-state Li-ion batteries were synthesized using a sol–gel method. This study investigated the impact of substituting Fe³⁺ (0.645 Å), a trivalent cation, for Ti⁴⁺ (0.605 Å) on ionic conductivity. Li_1+XFe_XTi_2-X(PO₄)₃ samples, subjected to various sintering temperatures, were characterized using TG-DTA, XRD with Rietveld refinement, XPS, FE-SEM, and AC impedance to evaluate composition, crystal structure, fracture-surface morphology, densification, and ionic conductivity. XRD analysis confirmed the formation of single-crystalline NASICON-type Li_1+XFe_XTi_2-X(PO₄)₃ at all sintering temperatures. However, impurities in the secondary phase emerged owing to the high sintering temperature above 1000 °C and increased Fe content. Sintered density increased with the densification of Li_1+XFe_XTi_2-X(PO₄)₃, as evidenced by FE-SEM observations of sharper edges of larger quasi-cubic grains at elevated sintering temperatures. At 1000 °C, with Fe content exceeding 0.4, grain coarsening resulted in additional grain boundaries and internal cracks, thereby reducing the sintered density. Li_1.3Fe_0.3Ti_1.7(PO₄)₃ sintered at 900 °C exhibited the highest density among the other conditions and achieved the maximum total ionic conductivity of 1.51 × 10⁻⁴ S/cm at room temperature, with the lowest activation energy for Li-ion transport at 0.37 eV. In contrast, Li_1.4Fe_0.4Ti_1.6(PO₄)₃ sintered at 1000 °C demonstrated reduced ionic conductivity owing to increased complex impedance associated with secondary phases and grain crack formation. Full article

This study employed the solid-state method to prepare perovskite-type high-entropy oxide materials La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃ and La(Co_0.2Cr_0.2Ni_0.2Ga_0.2Ge_0.2)O₃ with equimolar ratios at the B-site and explored the effects of sintering temperature on the phase structure and electrochemical properties of high-entropy oxide ceramics. The results show that after sintering at 1300$°\mathrm{C}$, both samples exhibit orthorhombic perovskite structures. Both have a relative density of >97%, while La(Co_0.2Cr_0.2Ni_0.2Ga_0.2Ge_0.2)O₃ has a significantly larger grain size. Using these materials as electrodes, the cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD) results indicate that the working electrode made of La(Co_0.2Cr_0.2Ni_0.2Ga_0.2Ge_0.2)O₃ shows higher oxidation reaction activity in CV measurements and achieved a specific capacitance of 74.3 F/g at a current density of 1 A/g in GCD measurements, which still maintained 73% of its initial specific capacitance (54.3 F/g) when the current density was increased to 10 A/g. Its capacitance retention rate is 10 percentage points higher than that of La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃ at high current densities, demonstrating superior rate performance. Full article

Batteries are used as energy storage devices in various equipment. Today, research is focused on solid-state batteries (SSBs), replacing the liquid electrolyte with a solid separator. The solid separators provide electrolyte stability, no leakage, and provide mechanical strength to the battery. Separators are mostly manufactured by either traditional processes or 3D printing technologies. These processes involve making a slurry of plastic, active and conductive material and usually adding a plasticizer when making thin films or filaments for 3D printing. This study investigates the additive manufacturing of solid-state electrolytes (SSEs) by employing fused deposition modeling (FDM) with recyclable, bio-derived polylactic acid (PLA) filaments. Precise control of macro-porosity is achieved by systematically varying key process parameters, including raster orientation, infill percentage, and interlayer adhesion conditions, thereby enabling the formation of tunable, interconnected pore networks within the polymer matrix. Following 3D printing, these engineered porous frameworks are infiltrated with lithium hexafluorophosphate (LiPF₆), which functions as the active ionic conductor. A tailored thermal sintering protocol is then applied to promote solid-phase fusion of the embedded salt throughout the macro-porous PLA scaffold, resulting in a mechanically robust and ionically conductive composite separator. The electrochemical ionic conductivity and structural integrity of the sintered SSEs are characterized through electrochemical impedance spectroscopy (EIS) and standardized mechanical testing to assess their suitability for integration into advanced solid-state battery architectures. The solid-state separator achieved an average ionic conductivity of 2.529 × 10⁻⁵ S·cm⁻¹. The integrated FDM-sintering process enhances ion exchange at the electrode–electrolyte interface, minimizes material waste, and supports cost-efficient, fully recyclable component fabrication. Full article

Multilayer ceramic lithium batteries (MLCBs) are regarded as a new type of oxide-based all-solid-state microbattery for integrated circuits and various wearable devices. The chemical compatibility between the solid electrolyte and electrode active materials during the high-temperature co-sintering process is crucial for determining the structural stability and cycling performance of MLCBs. This study focuses on the typical MLCB composite electrodes composed of the NASICON-type Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) solid electrolyte and the spinel-type Li₄Ti₅O₁₂ (LTO) anode material. The thermal behavior, phase structure, morphological evolution, and elemental chemical states of these composite electrodes were systematically investigated over a co-sintering temperature range of 400–900 °C. The results indicate that the reactivity between LATP and LTO during co-sintering is primarily driven by the diffusion of Li from the LTO anode, leading to the formation of TiO₂, Li₃PO₄, and LiTiOPO₄. Furthermore, the co-sintered LATP-LTO multilayer composites reveal that the generation of Li₃PO₄ at the LATP/LTO interface facilitates their co-sintering integration at 800–900 °C, which is essential for the successful fabrication of MLCBs. These findings provide direct evidence and valuable references for the structural and performance optimization of MLCBs in the future. Full article

The knowledge of Li diffusivities in electrode materials of Li-ion batteries (LIBs) is essential for a fundamental understanding of charging/discharging times, maximum capacities, stress formation and possible side reactions. The literature indicates that Li diffusion in the cathode material Li(Ni,Mn,Co)O₂ strongly increases during electrochemical delithiation. Such an increased Li diffusivity will be advantageous for performance if it is present already in the initial state after synthesis. In order to understand the influence of a varying initial Li content on Li diffusion, we performed Li tracer diffusion experiments on Li_xCoO₂ (LCO) and Li_xNi_1/3Mn_1/3Co_1/3O₂ (NMC, x = 1, 0.9, 0.65) cathode materials. The measurements were performed on polycrystalline sintered bulk materials, free of additives and binders, in order to study the intrinsic properties. The variation of Li content was achieved using reactive solid-state synthesis using pressed Li₂CO₃, NiO, Co₃O₄ and/or MnO₂ powders and high temperature sintering at 800 °C. XRD analyses showed that the resultant bulk samples exhibit the layered LCO or NMC phases with a low amount of cation intermixing. Moreover, the presence of additional NiO and Co₃O₄ phases was detected in NMC with a pronounced nominal Li deficiency of x = 0.65. As a tracer source, a ⁶Li tracer layer with the same chemical composition was deposited using ion beam sputtering. Secondary ion mass spectrometry in depth profile mode was used for isotopic analysis. The diffusivities followed the Arrhenius law with an activation enthalpy of about 0.8 eV and were nearly identical within error for all samples investigated in the temperature range up to 500 °C. For a diffusion mechanism based on structural Li vacancies, the results indicated that varying the Li content does not result in a change in the vacancy concentration. Consequently, the design and use of a cathode initially made of a Li-deficient material will not improve the kinetics of battery performance. The possible reasons for this unexpected result are discussed. Full article

Using the solid-state reaction technique, varied Y₂SiO₅ phosphors activated by europium (Eu³⁺) ions at varied concentrations were made at calcination temperatures of 1000 °C and 1250 °C during sintering in an air environment. The XRD technique identified the monoclinic structure, and the FTIR technique was used to analyze the generated phosphors. Photoluminescence emission and excitation patterns were measured using varying concentrations of Eu³⁺ ions. The optimal strength was observed at a 2.0 mol% concentration. Emission peaks were detected at 582 nm and 589 nm for the ⁵D₀→⁷F₁ transition and at 601 nm, 613 nm, and 632 nm for the ⁵D₀→⁷F₂ transition under 263 nm excitation. Because Eu³⁺ is naturally bright, these emission peaks show how ions change from one excited state to another. This makes them useful for making phosphors that emit red light for use in optoelectronics and flexible displays. Based on the computed (1931 CIE) chromaticity coordinates for the photoluminescence emission spectra, it was determined that the produced phosphor may be used in light-emitting diodes. The TL glow curve was examined for various doping ion concentrations and durations of UV exposure levels, revealing a broad peak at 183 °C. Using computerized glow curve deconvolution (CGCD), we calculated the kinetic parameters. Full article

Developing thin-film sheets made of oxide-based solid electrolytes is essential for fabricating surface-mounted ultracompact multilayer oxide solid-state batteries. To this end, solid-electrolyte slurry must be optimized for excellent dispersibility. Although oxide-based solid electrolytes for multilayer structures require sintering, high processing temperatures cause problems such as Li-ion volatilization and reactions with graphite anodes. Thus, low-temperature sinterable oxide-based solid-electrolyte materials should be devised. We successfully developed the conditions for producing thin films from 21 μm thick solid-electrolyte sheets of Li₂O-B₂O₃-Al₂O₃, one of the most promising candidates for multilayer solid-state batteries. A comprehensive analysis of the fabricated thin films included X-ray diffraction (XRD) to confirm their amorphous structure, scanning electron microscopy (SEM) for particle morphology, and contact angle measurements to verify surface hydrophilicity. Evaluation of a 32-layer bulk sample of solid-electrolyte sheets revealed an ionic conductivity of 2.33 × 10⁻⁷ S/cm and charge transfer resistance of 100.1 kΩ at a sintering temperature of 430 °C. Based on these results, cathode and anode active materials will be applied to develop high-energy-density multilayer ceramic batteries with hundreds of layers in future work. Full article