High-frequency electron paramagnetic resonance investigation of the Fe3+ impurity center in polycrystalline PbTiO3 in its ferroelectric phase

The intrinsic iron(III) impurity center in polycrystalline lead titanate was investigated by means of high-frequency electron paramagnetic resonance (EPR) spectroscopy in order to determine the local-environment sensitive fine structure parameter D. At a spectrometer frequency of 190 GHz, spectral analysis of a powder sample was unambiguously possible. The observed mean value D = +35.28 GHz can be rationalized if Fe3+ ions substitute for Ti4+ at the B-site of the perovskite ABO3 lattice forming a directly coordinated iron - oxygen vacancy defect associate. A consistent fit of the multi-frequency data necessitated use of a distribution of D values with a variance of about 1 GHz. This statistical distribution of values is probably related to more distant defects and vacancies.Comment: 6 pages, 3 figures, 1 table, to appear in J. App. Phys, 96 (2004

Effect of Nb-donor and Fe-acceptor dopants in (Bi1/2Na1/2)TiO3-BaTiO3-(K0.5Na0.5)NbO3 lead-free piezoceramics

The role of Fe as an acceptor and Nb as a donor in [0.94-x](Bi1/2Na1/2)TiO3-0.06BaTiO(3)-x (K0.5Na0.5)NbO3 (100xKNN) (x=0.02 and 0.03) lead-free piezoceramics was investigated. X-ray diffraction analyses show that all the profiles are best-fitted with a cubic symmetry where Fe doping tends to induce a lattice expansion, while Nb doping does the opposite. The strain and polarization characteristics are enhanced and suppressed by the acceptor and donor dopants, respectively. The improvement in the electrical properties with acceptor doping is accompanied by the stabilization of a ferroelectric order. Electron paramagnetic resonance spectroscopic analysis suggests that the stabilization of the ferroelectric order by the Fe dopant originates from the formation of (Fe-Ti'-V-O(center dot center dot))(center dot) defect dipoles.open211

High-Frequency EPR Analysis of MnO2-Doped [Bi0.5Na0.5]TiO3-BaTiO3 Piezoelectric Ceramics - Manganese Oxidation States and Materials 'Hardening'

High-frequency electron paramagnetic resonance (EPR) has been used to identify different manganese oxidation states in the 0.5 mol% MnO2-doped (100-x)Bi0.5Na0.5TiO3-xBaTiO(3) (BNT-xBT) solid solution with x = 6. The as-sintered and air-annealed samples show two distinct EPR resonances that were assigned to Mn2+- and Mn3+ -ions, respectively, incorporated at the Ti-site. The equilibrium between acceptor-type Mn ''(Ti)- and Mn'(Ti)-states can be explained by the thermodynamic equilibration under air at the sintering temperature corresponding to [n] > [p], which yields an n-type Mn:BNT-6BT compound.close2

Sulfur Reduction Reaction in Lithium-Sulfur Batteries: Mechanisms, Catalysts, and Characterization

Lithium–sulfur batteries are one of the most promising alternatives for advanced battery systems due to the merits of extraordinary theoretical specific energy density, abundant resources, environmental friendliness, and high safety. However, the sluggish sulfur reduction reaction (SRR) kinetics results in poor sulfur utilization, which seriously hampers the electrochemical performance of Li–S batteries. It is critical to reveal the underlying reaction mechanisms and accelerate the SRR kinetics. Herein, the critical issues of SRR in Li–S batteries are reviewed. The conversion mechanisms and reaction pathways of sulfur reduction are initially introduced to give an overview of the SRR. Subsequently, recent advances in catalyst materials that can accelerate the SRR kinetics are summarized in detail, including carbon, metal compounds, metals, and single atoms. Besides, various characterization approaches for SRR are discussed, which can be divided into three categories: electrochemical measurements, spectroscopic techniques, and theoretical calculations. Finally, the conclusion and outlook part gives a summary and proposes several key points for future investigations on the mechanisms of the SRR and catalyst activities. This review can provide cutting-edge insights into the SRR in Li–S batteries

Influence of the SEI Formation on the Stability and Lithium Diffusion in Si Electrodes

Silicon (Si) is an attractive anode material for Li-ion batteries (LIBs) due to its high theoretical specific capacity. However, the solid-electrolyte interphase (SEI) formation, caused by liquid electrolyte decomposition, often befalls Si electrodes. The SEI layer is less Li-ion conductive, which would significantly inhibit Li-ion transport and delay the reaction kinetics. Understanding the interaction between the SEI components and Li-ion diffusion is crucial for further improving the cycling performance of Si. Herein, different liquid electrolytes are applied to investigate the induced SEI components, structures, and their role in Li-ion transport. It is found that Si electrodes exhibit higher discharge capacities in LiClO4-based electrolytes than in LiPF6-based electrolytes. This behavior suggests that a denser and more conductive SEI layer is formed in LiClO4-based electrolytes. In addition, a coating of a Li3PO4 artificial SEI layer on Si suppresses the formation of natural SEI formation, leading to higher capacity retentions. Furthermore, galvanostatic intermittent titration technique (GITT) measurements are applied to calculate Li-ion diffusion coefficients, which are found in the range of 10(-23)-10(-19) m(2)/s

CuO as a sintering additive for (Bi1/2Na1/2)TiO3-BaTiO3- (K0.5Na0.5)NbO3 lead-free piezoceramics

CuO as a sintering additive was utilized to explore a low-temperature sintering of 0.92(Bi1/2Na1/2)TiO3-0.06BaTiO(3)-0.02(K0.5Na0.5)NbO3 lead-free piezoceramic which has shown a promise for actuator applications due to its large strain. The sintering temperature guaranteeing the relative density of greater than 98% is drastically decreased with CuO addition, and saturates at a temperature as low as similar to 930 degrees C when the addition level exceeds ca. 1 mol.%. Two distinguished features induced by the addition of CuO were noted. Firstly, the initially existing two-phase mixture gradually evolves into a rhombohedral single phase with an extremely small non-cubic distortion. Secondly, a liquid phase induced by the addition of CuO causes an abnormal grain growth, which can be attributed to the grain boundary reentrant edge mechanism. Based on these two observations, it is concluded that the added CuO not only forms a liquid phase but also diffuses into the lattice. In the meantime, temperature dependent permittivity measurements both on unpoled and poled samples suggest that the phase stability of the system is greatly influenced by the addition of CuO. Polarization and strain hysteresis measurements relate the changes in the phase stability closely to the stabilization of ferroelectric order, as exemplified by a significant increase in both the remanent strain and polarization values. Electron paramagnetic resonance (EPR) spectroscopic analysis revealed that the stabilization of ferroelectric order originates from a significant amount of Cu2+ diffusing into the lattice on B-site. There, it acts as an acceptor and forms a defect dipole in association with a charge balancing oxygen vacancy.close151

Interface Aspects in All-Solid-State Li-Based Batteries Reviewed

Extensive efforts have been made to improve the Li-ionic conductivity of solid electrolytes (SE) for developing promising all-solid-state Li-based batteries (ASSB). Recent studies suggest that minimizing the existing interface problems is even more important than maximizing the conductivity of SE. Interfaces are essential in ASSB, and their properties significantly influence the battery performance. Interface problems, arising from both physical and (electro)chemical material properties, can significantly inhibit the transport of electrons and Li-ions in ASSB. Consequently, interface problems may result in interlayer formation, high impedances, immobilization of moveable Li-ions, loss of active host sites available to accommodate Li-ions, and Li-dendrite formation, all causing significant storage capacity losses and ultimately battery failures. The characteristic differences of interfaces between liquid- and solid-type Li-based batteries are presented here. Interface types, interlayer origin, physical and chemical structures, properties, time evolution, complex interrelations between various factors, and promising interfacial tailoring approaches are reviewed. Furthermore, recent advances in the interface-sensitive or depth-resolved analytical tools that can provide mechanistic insights into the interlayer formation and strategies to tailor the interlayer formation, composition, and properties are discussed.</p