Lead Titanate Research Articles

A Bandgap‐Tuned Tetragonal Perovskite as Zero‐Strain Anode for Potassium‐Ion Batteries

AbstractPIBs are emerging as a promising energy storage system due to high abundance of potassium resources and theoretical energy density, however, progress of PIBs is severely hindered by structural instability and poor cycling of anode material during continual insertion and extraction of larger‐sized K+. Hence, developing anode material with structural stability and stable cycling remains a great challenge. Herein, band gap‐tuned Mo‐doped and carbon‐coated lead titanate (CMPTO) with zero‐strain K+ storage is presented as ultra‐stable PIBs anode. Mo doping introduces narrowed band gap and optimized crystal lattice for enhanced intrinsic electron and ion transfer. Demonstrated by in situ XRD characterizations, the crystal structure stays stable with unchanged peak positions, fully revealing zero‐strain characteristic of CMPTO anode during potassium storage for stable cyclic capability. Ultimately, CMPTO anode achieved ultra‐stable cycling performance of 7000 cycles at 500 mA g−1 with high capacity retention of 90 % and considerable specific capacity of 130.9 mAh g−1 after 600 cycles at 100 mA g−1; with relatively large density, CMPTO realized eminent volumetric capacity of 1111.09 mAh cm−3 and ultra‐long cycling life of 10000 cycles at 7041 mA cm−3. This work introduces a promisingly new route into developing anode materials with ultra‐stable performance for PIBs.

A Bandgap-Tuned Tetragonal Perovskite as Zero-Strain Anode for Potassium-Ion Batteries.

PIBs are emerging as a promising energy storage system due to high abundance of potassium resources and theoretical energy density, however, progress of PIBs is severely hindered by structural instability and poor cycling of anode material during continual insertion and extraction of larger-sized K+. Hence, developing anode material with structural stability and stable cycling remains a great challenge. Herein, bandgap-tuned Mo-doped and carbon-coated lead titanate (CMPTO) with zero-strain K+ storage is presented as ultra-stable PIBs anode. Mo doping introduces narrowed bandgap and optimized crystal lattice for enhanced intrinsic electron and ion transfer. Demonstrated by in situ XRD characterizations, the crystal structure stays stable with unchanged peak positions, fully revealing zero-strain characteristic of CMPTO anode during potassium storage for stable cyclic capability. Ultimately, CMPTO anode achieved ultra-stable cycling performance of 7000 cycles at 500 mA g-1 with high capacity retention of 90% and considerable specific capacity of 130.9 mAh g-1 after 600 cycles at 100 mA g-1; with relatively large density, CMPTO realized eminent volumetric capacity of 1111.09 mAh cm-3 and ultra-long cycling life of 10000 cycles at 7041 mA cm-3. This work introduces a promisingly new route into developing anode materials with ultra-stable performance for PIBs.

Evaluating the significance of rare earth and iron doping on structure-property of lead titanate

The samples (Pb0.8Ln0.2 Fe0.2 Ti0.8O3, (Ln= La, Nd, Sm, Gd)) were synthesized successfully by mixed oxide method. A significant reduction in tetragonality is observed with the modification of structure. The grain size from FESEM study was observed to be decreasing with increase in ionic radii of rare earth ions. Specifically, the dielectric constant is found to be maximum for the Sm-doped sample. Conductivity studies at varying temperature and frequencies reveal the NTCR behaviour of these samples. In Sm, Nd and Gd doped samples, tunnelling of small polarons is responsible for conduction process whereas for La doped sample, the conduction process is mediated through the combined effect of small polaron tunnelling and bipolaron hopping. The Sm-doped sample exhibits highest remanent polarization. All the results of this comprehensive study provide valuable insights into the effect of dopant ions on various properties of the studied materials, paving the way for device applications.

Origins of the large piezoelectric response of samarium-doped lead magnesium niobate–lead titanate ceramics

Origins of the large piezoelectric response of samarium-doped lead magnesium niobate–lead titanate ceramics

Composite based on Poly(ethylene-co-vinyl acetate) with lead-titanate for gamma attenuation

The radioprotective ability of composite materials based on a poly (ethylene-co-vinyl acetate) matrix with dispersed lead titanate filler has been estimated. The filler was obtained from the environmentally friendly synthesis based on exchanging potassium ions for lead in potassium titanates. The gamma ray protective composites have low density, good mechanical qualities and are able to be reprocessed by high-performance extrusion or injection molding techniques. The present work is dedicated to assess mechanical and gamma ray shielding properties of poly (ethylene-vinyl acetate) composites with different lead titanate content (70, 80 and 90 wt percent of lead titanate). The study was carried out for the emission of 137Cs, 60Co and 241Am isotopes with energies 0.6617 MeV, 1.332/1.173 MeV and 0.0595 MeV respectively. The study of radiation-protective properties showed that for 137Cs radiation half value layer for the composite containing 90 wt% of lead titanate is three times higher than for neat lead: 2.1 and 0.7 cm respectively. For the 60Co emission, these values are more close: 1.9 cm for 90 wt% composite and 1.2 cm for lead. The layer of 0.5 cm of composite with 70 % lead titanate almost fully diminishes the low-energetic 241Am radiation, and hence, is superior to lead foil of the same length. Mass attenuation coefficients of 70% composite for 0.6617 MeV, 1.332/1.173 MeV and 0.0595 MeV are 0.088, 0.046 and 2.487 cm2/g respectively. The tensile elongation at fracture decrease is 460% for 70/30 lead titanate/poly (ethylene-vinyl acetate) and is equal to 6% for 90/10 lead titanate/poly (ethylene-vinyl acetate).

Lithium lead titanate (Li2PbxTi1-xO3, 0.1

Tritium breeder is an important functional material in d-T fusion reactor blanket serving the purpose of tritium re-production and energy conversion. Presently, Li2TiO3 ceramics is considered as the most promising solid tritium breeder for its good chemical stability, high mechanical strength and excellent tritium release performance. However, low lithium content and lithium evaporation at high temperature lead to a low tritium breeding ratio. In the paper the neutron multiplier element, Pb, is introduced into Li2TiO3 to obtain lithium lead titanate (Li2PbxTi1-xO3) as tritium breeder, which combined the advantages of Pb and Li2TiO3 ceramic. Li2PbxTi1-xO3 powders were synthesized via a sol-gel method, employing lithium acetate, tetrabutyl titanate, and lead acetate, with varying lead contents. The characterization results indicate that at a molar ratio of titanium to lead of 1:2, Li2TiO3-Li2PbO3 eutectic phase could be formed. The tritium breeding ratio (TBR) of Li2PbxTi1-xO3 materials were evaluated by Monte Carlo Code, which was notably influenced by the lead content, exhibiting a continuous increase with higher Pb content and neutron energy. The Li2PbxTi1-xO3 pebbles were prepared by freeze-drying route. The mechanical strength of Li2PbxTi1-xO3 pebbles could be affected significantly by the lead content. Compared to the conventional Li2TiO3 ceramics, the Li2Pb0.4Ti0.6O3 ceramics exhibits a higher crushing load of 25.33 N.

Multistep polarization switching and reduced coercive field in lead titanate thin films

Multistep polarization switching and reduced coercive field in lead titanate thin films

Tailoring perovskite ceramics for improved structure, vibrational behaviors and radiation protection: The role of lanthanum in PbTiO3

This study investigates the characteristics of lanthanum (La)-doped lead titanate (PbLaxTi(1-3x/4)O3 where, x = 0.0, 0.02, 0.04, 0.06, 0.08, and 0.1), a type of perovskite ceramic. It specifically focuses on analyzing its structure, vibrational properties, and efficacy in shielding against radiation. The prepared samples are investigated by X-ray diffraction (XRD), which clarified that the small doping of La (x ≤ 0.06) produced the required phase, and increasing the La doping (x > 0.06) produced nonrequired phases (secondary phase). Also, increasing the La doping converted the crystal symmetry from tetragonal to cubic, which was confirmed by the tetragonality raio (c/a) calculations. Also, the samples are investigated by Fourier transform infrared (FTIR) spectroscopy to confirm the XRD results. Transmission electron microscopy (TEM) examination clarified that the prepared samples were in the nanoscale range with a maximum crystallite size value of around 70 nm. In addition, the shielding effectiveness of all the prepared samples was theoretically evaluated using the Phy-X/PDS program by considering characteristics such as the linear attenuation coefficient (GLAC), mean free path (GMFP), transmission factor (TF), and radiation protection efficiency (RPE). Increasing the La concentration increases the theoretical density to 4.98 gm/cm3 at x = 0.1, leading to low TF and GMFP values and high GLAC values. This produces samples with high attenuation to radiation and high shielding effectiveness.

Single Source Precursor Synthesis of Lead Titanate (PbTiO3) for the Electrochemical Detection of Nitric Oxide (NO)

Electrochemical detection of Nitric oxide (NO) has attracted considerable attention due to its central role in different processes of mammalian physiology. In this study, NO is electrochemically detected using lead titanate (PbTiO3) as an electrochemical sensor. The lead titanate (PbTiO3) was prepared successfully through thermal decomposition of bimetallic complex [PbTi(O2CCF3)4(THF)3O]2 containing both lead and titanium metals. A phase of synthesized PbTiO3 powder was studied using X-ray diffraction spectroscopy and Raman spectroscopy, while the morphology and crystallite size were studied by field emission scanning electron microscopy and high-resolution transmission electron microscopy. Further, X-ray photoelectron spectroscopy analysis was also done to determine the elemental composition along with their oxidation states. Finally, the PbTiO3 powder was coated on GCE (glassy carbon electrode) and then further studied electrochemically for sensing NO in NaNO2 solution at pH = 2.5. Moreover, the detection capability of PbTiO3 was analyzed upon adding different concentrations of 1 to 10 mM of NaNO2. As a result, current and concentration followed a linear response. For the interferent studies, uric acid, glucose, dopamine, and ascorbic acid were used as interferents. It was noted that no signals appeared with these interferents in the voltammogram.

Perovskite ceramics: the impact of lanthanum doping on the structural, radiation shielding and vibrational characteristics of lead titanate

Perovskite ceramics: the impact of lanthanum doping on the structural, radiation shielding and vibrational characteristics of lead titanate

Ab initio generalized Langevin equation

We introduce a machine learning-based approach called ab initio generalized Langevin equation (AIGLE) to model the dynamics of slow collective variables (CVs) in materials and molecules. In this scheme, the parameters are learned from atomistic simulations based on ab initio quantum mechanical models. Force field, memory kernel, and noise generator are constructed in the context of the Mori-Zwanzig formalism, under the constraint of the fluctuation-dissipation theorem. Combined with deep potential molecular dynamics and electronic density functional theory, this approach opens the way to multiscale modeling in a variety of situations. Here, we demonstrate this capability with a study of two mesoscale processes in crystalline lead titanate, namely the field-driven dynamics of a planar ferroelectric domain wall, and the dynamics of an extensive lattice of coarse-grained electric dipoles. In the first case, AIGLE extends the reach of ab initio simulations to a regime of noise-driven motions not accessible to molecular dynamics. In the second case, AIGLE deals with an extensive set of CVs by adopting a local approximation for the memory kernel and retaining only short-range noise correlations. The scheme is computationally more efficient than molecular dynamics by several orders of magnitude and mimics the microscopic dynamics at low frequencies where it reproduces accurately the dominant far-infrared absorption frequency.

Optical and ferroelectric properties of lead titanate nanocrystals dispersed within borate glass matrix

Lead titanate nanocrystals dispersed within the borate glass matrix (composite) with the composition 75 B2O3-25 PbTiO3 (in mol %) was prepared. The composite's XRD analysis indicated it contains glassy phase, and this was further confirmed by DSC study. TEM, SAED, and FTIR analyses provided evidence that the PbTiO3 nanocrystals dispersed within the borate glass matrix, establishing the composite nature of this sample. The average particle size found of PbTiO3 was determined to be 57.2 nm via TEM. The composite's FTIR analysis indicated the presence of BO3 with NBO's, and BO4 units. Additionally, the presence of the Ti3+ ions in TiO6 units as well as Ti4+ ions in TiO4 and TiO6 units. The Curie temperature (Tc) of PbTiO3 in present composite sample was confirmed through both DSC and dielectric studies. Optical analysis of this composite sample unveiled three transmission bands, one corresponding to the 3Γ5 →2Γ3 charge transfer transition between Ti3+ and Ti4+ions. While the other transitions 2B2g →2B1g and 2B2g →2A1g are corresponding to the octahedral of Ti3+ (3d1) ions in tetragonal distorted sites. The polarization-field (P-E) loops of this composite sample at various electric fields unveiled relatively narrow hysteresis loops.

Magnetron-Sputtered Lead Titanate Thin Films for Pyroelectric Applications: Part 2-Electrical Characteristics and Characterization Methods.

Pyroelectric materials are naturally electrically polarized and exhibits a built-in spontaneous polarization in their unit cell structure even in the absence of any externally applied electric field. These materials are regarded as one of the ideal detector elements for infrared applications because they have a fast response time and uniform sensitivity at room temperature across all wavelengths. Crystals of the perovskite lead titanate (PbTiO3) family show pyroelectric characteristics and undergo structural phase transitions. They have a high Curie temperature (the temperature at which the material changes from the ferroelectric (polar) to the paraelectric (nonpolar) phase), high pyroelectric coefficient, high spontaneous polarization, low dielectric constant, and constitute important component materials not only useful for infrared detection, but also with vast applications in electronic, optic, and MEMS devices. However, the preparation of large perfect and pure single crystals PbTiO3 is challenging. Additionally, difficulties arise in the application of such bulk crystals in terms of connection to processing circuits, large size, and high voltages required for their operation. In this part of the review paper, we explain the electrical behavior and characterization techniques commonly utilized to unravel the pyroelectric properties of lead titanate and its derivatives. Further, it explains how the material preparation techniques affect the electrical characteristics of resulting thin films. It also provides an in-depth discussion of the measurement of pyroelectric coefficients using different techniques.

Magnetron Sputtered Lead Titanates Thin Films for Pyroelectric Applications: Part 1: Epitaxial Growth, Material Characterization.

Pyroelectric materials, are those materials with the property that in the absence of any externally applied electric field, develop a built-in spontaneous polarization in their unit cell structure. They are regarded as ideal detector elements for infrared applications because they can provide fast response time and uniform sensitivity at room temperature over all wavelengths. Crystals of the perovskite Lead Titanate (PbTiO3) family show pyroelectric characteristics and undergo structural phase transitions. They have a high Curie temperature (the temperature at which the material changes from the ferroelectric (polar) to the paraelectric (nonpolar) phase), high pyroelectric coefficient, high spontaneous polarization, low dielectric constant, and constitute important component materials not only useful for infrared detection, but also with vast applications in electronic, optic, and Micro-electromechanical systems (MEMS) devices. However, the preparation of large perfect, and pure single crystals of PbTiO3 is challenging. Additionally, difficulties arise in the application of such bulk crystals in terms of connection to processing circuits, large size, and high voltages required for their operation. A number of thin film fabrication techniques have been proposed to overcome these inadequacies, among which, magnetron sputtering has demonstrated many potentials. By addressing these aspects, the review article aims to contribute to the understanding of the challenges in the field of pyroelectric materials, highlight potential solutions, and showcase the advancements and potentials of pyroelectric perovskite series including PbZrTiO3 (PZT), PbxCa1-x (PZN-PT), etc. for which PbTiO3 is the end member. The review is presented in two parts. Part 1 focuses on material aspects, including preparation methods using magnetron sputtering and material characterization. We take a tutorial approach to discuss the progress made in epitaxial growth of lead titanate-based ceramics prepared by magnetron sputtering and examine how processing conditions may affect the crystalline quality of the growing film by linking to the properties of the substrate/buffer layer, growth substrate temperature, and the oxygen partial pressure in the gas mixture. Careful control and optimization of these parameters are crucial for achieving high-quality thin films with desired structural and morphological characteristics.

Influence of the Annealing Environment on the Structure and Ferroelectric Properties of Lead Titanate Thin Films

Lead titanate thin films of pyrochlore phase were deposited using layer-by-layer reactive magnetron sputtering on a heated platinized silicon substrate. It was found that the pyrochlore phase transition to the perovskite phase was initiated at 700 °C, and the properties of the PbTiO3 films could be controlled by changing the annealing environment. The thin films annealed in air and oxygen environments (1.33 Pa) have a tetragonal structure. The highest values of remnant polarization and the coercive field were 38 μC/cm2 and 130 kV/cm, respectively, but the largest dielectric loss was determined for the films annealed in air. The remnant polarization, coercive field and dielectric loss were reduced when the annealing of films was performed using oxygen gas at 1.33 Pa pressure. The films annealed in vacuum showed a rhombohedral (and ferroelectric) structure with the lowest remnant polarization and coercive field values. Such a structure was not observed for lead titanate at room temperature. It was observed that the surface morphology strongly depended on the reaction rate, which was influenced by the oxygen concentration in the environment.

Structural description of temperature evolution of polar clusters in PLZT relaxor ceramics

ABSTRACT This letter quantifies the phases by Rietveld refinement of perovskite relaxor ferroelectric ceramics of lanthanum-modified lead titanate zirconate (PLZT 9/65/35) as a function of temperature. The refinement results show the relative limit of phases between the polar electrical percolation and their vanishing as a function of temperature, coincident with dielectric measurements. The quantification of polar/nonpolar phases simultaneously is structural description of the polar clusters in relaxor ferroelectrics ceramics. The temperature changes in the polar/nonpolar phase ratio suggest a volume dynamism of the polar clusters as a function of temperature.

Preparation of a Novel Nanostructured Lead Titanate Composite Photocatalyst and Its Degradation of Organic Dyes under Visible Light

Photocatalytic dye degradation is an energy-saving, environmentally friendly and sustainable way of managing potentially toxic wastewater from the textile industry. PbTiO3 was prepared using a solid-state reaction method, and an optimal ratio of PbTiO3/TiO2/g-C3N4 photocatalyst was synthesized using the sol-gel method to test its ability to decompose organic dyes. Methylene blue (MB) was selected as a target dye to test the photocatalytic effects. SEM results showed that the synthesis of a PbTiO3/TiO2/g-C3N4 photocatalyst yielded a unique nano structure with many surface pores. UV-Vis analysis demonstrated that the novel composite photocatalyst had higher visible light absorption, and a reduced energy gap. Experimental results showed that of the samples tested, PTO/TO/CN 1.0 showed the best photocatalytic effect on the removal of MB. Under visible light, the removal rate of MB by PTO/TO/CN 1.0 was up to 98.79%. The novel PTO/TO/CN 1.0 photocatalyst exhibited relatively high MB adsorption and had a high photocatalytic ability.

Relative Investigation on Microwave-Assisted Zr-Modified PbTiO3 and BaTiO3 Ferroelectric Ceramics for Energy Storage Application.

The escalating demand for energy-related devices has prompted an intensive study on materials for energy harvesting and storage. Recently, due to the toxicity of lead-based materials, researchers have drawn their attention to lead-free ferroelectrics. However, it is indisputable that commercially lead zirconium titanate (PZT) has gained an irreplaceable position as an actuator. In the present work, we specifically compare microwave-sintered PbZr0.52Ti0.48O3 and BaZr0.20Ti0.80O3 ceramics based on their energy-storage capacity. The structural, optical, electrical, ferroelectric, and energy storage properties of microwave-sintered Zr-modified lead titanate (PbZr0.52Ti0.48O3, PZT) and Zr-modified barium titanate (BaZr0.20Ti0.80O3, BZT) ceramics are investigated and addressed. The temperature-dependent dielectric property analysis suggests high transition temperature and dielectric properties for PZT ceramic, whereas the near-room temperature transition is observed in the case of BZT. Furthermore, the band-gap energy value of BZT and PZT from UV-vis spectroscopy indicates the possible use of these ceramics in optoelectronic devices. The ferroelectric properties of PZT and BZT are discussed, and the maximum energy storage capacities are found to be 30.5 and 21 mJ/cm3 for PZT and BZT, respectively. It is found that microwave-sintered PZT's characteristics make it an attractive option for use in filters, phase shifters, sensors, actuators, and energy-related devices. On the other hand, BZT finds its suitability in biomedical devices and underwater applications.

Electrical and dielectric properties of EVA/modified lead titanate elastomer composites

At first, the modified lead titanate (PWNTO) was synthesised by cost-effective solid-state reaction method.The ethylene–vinyl acetate (EVA)/PWNTO polymer composites with 2.5, 5.0, 7.5 and 10.0 wt% of PWNTO were fabricated by the solution casting method. The present communication highlights the dielectric behaviour, ac conductivity, impedance of these elastomer composite-sheets. As the inorganic filler content increases in the elastomer-system of EVA/PWNTO, the relative dielectric constant increases. The ac-conductivity of the above films also increasing in the frequency 1kHz to 1 MHz. The behaviour of the Nyquist-plot is simulated with an equivalent circuit of (CQR)(CR); from this the parameters like the bulk capacitance (Cb), bulk resistance (Rb) and frequency factor(n) were evaluated.

Exploring the tunability of lead free Ba0.5Sn0.5TiO3 to mimic PbTiO3

Can a material be designed and engineered to use as a replacement for an environmentally unfriendly material? In the specific context of lead titanates, the quest for finding such material replacements is ongoing, beginning from lead free alternatives with simple perovskite compositions, extending to hybrid and double perovskite compositions. In this work, we have demonstrated through ab initio density functional theory investigations the tunability of multiple properties of a simple perovskite Ba0.5Sn0.5TiO3 to mimic that of PbTiO3. Our results show that A-site Sn enhances the polarization of Ba0.5Sn0.5TiO3 closer to that of PbTiO3 and tunes its pressure dependent polarization behavior to become similar to that of PbTiO3 and dissimilar to that of BaTiO3 by reorienting the displacements profiles of A, B site and O atoms to become like that of their counterparts in PbTiO3. Compressive pressures facilitate transition from indirect to direct bandgap, increase the mobility of charge carriers and lead to stronger exciton binding in Ba0.5Sn0.5TiO3 opening up its use for optoelectronics. Ba0.5Sn0.5TiO3 has an early onset of absorption and its absorption spectra in UV range is qualitatively similar to PbTiO3 albeit with reduced absorption peak heights and broadening. The absorption spectra of Ba0.5Sn0.5TiO3 can be modified via application of strains and peak absorption heights can be changed to become similar to that of PbTiO3. We also demonstrate that the dielectric constant as well as refractive index of Ba0.5Sn0.5TiO3 can be modulated to increase (decrease) by applying compressive (tensile) strains. The study of mechanical properties demonstrates that Ba0.5Sn0.5TiO3 is more ductile and is mechanically stable even under higher compressive strains making it excitingly attractive for device applications over other lead-free alternatives that are known to display poor stabilities. These comprehensive investigations demonstrate for the first time that all the physical properties of Ba0.5Sn0.5TiO3 can be tuned as desired for a chosen device application making it a competitive and green replacement to lead titanates.