A Feasible Dual Modification Strategy of Internal Anion Redox Chemistry and Surface Engineering on P2 Layer-Structured Cathodes in Sodium-Ion Batteries.

Boosting the anion redox reaction opens up a possibility of further capacity enhancement on transition-metal-ion redox-only layer-structured cathodes for sodium-ion batteries. To mitigate the deteriorating impact on the internal and surface structure of the cathode caused by the inevitable increase in the operation voltage, probing a solution to promote the bulk-phase crystal structure stability and surface chemistry environment to further facilitate the electrochemical performance enhancement is a key issue. A dual modification strategy of establishing an anion redox hybrid activation trigger agent inside the crystal structure in combination with surface oxide coating is successfully developed. P2-type layer structure cathode materials with Zn/Li (Na-O-Zn@Na-O-Li) anion redox hybrid triggers and a ZnO coating layer possess superior capacity and cycle performance, along with outstanding structural stability, decreased Mn-ion dissolution effect, and less crystal particle cracking during the cycling process. This study represents a facile modification solution to perform structure optimization and property enhancement toward high-performance layered structure cathode materials with anion redox features in sodium-ion batteries.

High DC-Bias Stability and Reliability in BaTiO3-Based Multilayer Ceramic Capacitors: The Role of the Core-Shell Structure and the Electrode.

With the miniaturization of multilayer ceramic capacitors (MLCCs) and the increase of the electric field on a single dielectric layer, dielectric constant DC-bias stability and reliability have gradually aroused attention in the advanced electronics industry. In this study, MLCCs with outstanding DC-bias stability and reliability were prepared by using dielectric ceramic optimization and electrode optimization strategies. The effect of the Dy-Y doping concentration on the microstructure, dielectric properties, and reliability of BaTiO3-based ceramics was investigated. The shell ratio and effective shell doping concentration of the core-shell structure in ceramic grains play important roles in defects and electrical performances. The ceramic with appropriate doping contents shows a dielectric constant of 1800 and a dielectric constant change rate of -17% under a DC field of 4 kV/mm, which was fabricated into prototype MLCCs with different Ni electrodes. MLCCs exhibit outstanding DC-bias stability with a -28% degradation in the dielectric constant under a DC field of 4 kV/mm while possessing a dielectric constant of 2300 and satisfying the EIA X7S specification. Additionally, it was discovered that MLCCs prepared by using fine-size Ni particle electrodes have low electrode roughness and high interfacial Schottky barriers, resulting in better reliability. This study provides promising candidate materials and theoretical references for high-end and high DC-bias stability MLCCs.

Effective and Low-Cost In Situ Surface Engineering Strategy to Enhance the Interface Stability of an Ultrahigh Ni-Rich NCMA Cathode.

Ultrahigh Ni-rich quaternary layered oxides LiNi1-x-y-zCoxMnyAlzO2 (1 - x - y - z ≥ 0.9) are regarded as some of the most promising cathode candidates for lithium-ion batteries (LIBs) because of their high energy density and low cost. However, poor rate capacity and cycling performance severely limit their further commercial applications. Herein, an in situ coating strategy is developed to construct a uniform LiAlO2 layer. The NH4HCO3 solution is added to a NaAlO2 solution to form a weak alkaline condition, which can reduce the hydrolysis rate of NaAlO2, thus enabling uniform deposition of Al(OH)3 on the surface of a Ni0.9Co0.07Mn0.01Al0.02(OH)2 (NCMA) precursor. The LiAlO2-coated samples show enhanced cycling stability and rate capacity. The capacity retention of NCMA increases from 70.7% to 88.3% after 100 cycles at 1 C with an optimized LiAlO2 coating amount of 3 wt %. Moreover, the 3 wt % LiAlO2-coated sample also delivers a better rate capacity of 162 mAh g-1 at 5 C, while that of an uncoated sample is only 144 mAh g-1. Such a large improvement of the electrochemical performance should be attributed to the fact that a uniform LiAlO2 coating relieves harmful interfacial parasitic reactions and stabilizes the interface structure. Therefore, this in situ coating approach is a viable idea for the design of higher-energy-density cathode materials.

Synergistic Effect of Microstructure Engineering and Local Crystal Structure Tuning to Improve the Cycling Stability of Ni-Rich Cathodes.

Ultrahigh Ni-rich layered oxides have been regarded as one of the most promising cathode candidates. However, cycling instability induced by interfacial reactions and irreversible H2-H3 lattice distortion is yet to be demonstrated by an effective strategy that could construct a stable grain interface and microstructure. Here, Ni-rich cathode LiNi0.92Co0.05Mn0.03O2 is modified by B and Ti to realize the synchronous regulation of a microstructure and the oxygen framework robustness. Compared with the large equiaxed crystalline grains for the pristine cathode, highly elongated grains with a strong radially oriented crystallographic texture in which the (003) facet is maximized are produced for Ti and B-modified LiNi0.92Co0.05Mn0.03O2. With the suppressed H2-H3 phase transition and cation mixing provided by radially oriented grains and turned local crystal oxygen framework robustness during cycling, the co-modified cathode exhibits enhanced Li+ diffusion kinetics and a capacity retention of 78.3% after 100 cycles, which outperformed the 38.5% for the pristine cathode. The improved cycling performance suggests the significance of the turned microstructure and local crystal structure in suppressing internal strain and crystal structure degradation. The synchronous realization of microstructure engineering and local crystal structure turning by optimal element combination would provide a heuristic solution for the construction of high perform Ni-rich cathodes.

Multiphase Engineered BNT-Based Ceramics with Simultaneous High Polarization and Superior Breakdown Strength for Energy Storage Applications.

Dielectric ceramics are crucial for high-temperature, pulse-power energy storage applications. However, the mutual restriction between the polarization and breakdown strength has been a significant challenge. Here, multiphase engineering controlled by the two-step sintering heating rate is adopted to simultaneously obtain a high polarization and breakdown strength in 0.8(0.95Bi0.5Na0.5TiO3-0.05SrZrO3)-0.2NaNbO3 (BNTSZNN) ceramic systems. The coexistence of tetragonal (T) and rhombohedral (R) phases benefits the temperature stability of BNTSZNN ceramics. Increasing the heating rate during sintering reduces the diffusion of SrZrO3 and NaNbO3 into Bi0.5Na0.5TiO3, which results in a high proportion of the R phase and a finer grain size. The overall polarization is enhanced by increasing the proportion of the high-polarization R phase, which is demonstrated using a first-principles method. Meanwhile, the finer grain size enhances the breakdown strength. Following this design philosophy, an ultrahigh Wdis of 5.55 J/cm3 and η above 85% is achieved in BNTSZNN ceramics as prepared with a fast heating rate of 60 °C/min given a simultaneously high polarization of 43 µC/cm2 and high breakdown strength of 350 kV/cm. Variations in the discharge energy density from room temperature to 160 °C are less than 10%. Additionally, such BNTSZNN ceramics exhibit an ultrafast discharge speed with τ0.9 at approximately 60 ns, which shows great potential in pulse-power system applications.

Phase-field modeling of the coupled domain structure and dielectric breakdown evolution in a ferroelectric single crystal.

The study of domain switching and dielectric breakdown behavior of ferroelectrics together with their relations is crucial for understanding the essence of ferroelectric physics and exploring their applications. In this work, a phase-field method is developed to reveal the coupled domain structure and dielectric breakdown evolution in a ferroelectric single crystal (FSC) by employing the Ginzburg-Landau kinetic equation and Griffith type energy criterion. Results show that the domain switching mobility, symbolizing the speed of polarization evolution, has a significant influence on ferroelectric properties, namely coercive field, dielectric breakdown strength (DBS), discharge energy density (DED), and energy storage efficiency (ESE). It is found that FSC with the higher domain switching mobility always displays a lower coercive field and smaller remanent electric displacement (or polarization) together with a higher DBS, accounting for a higher DED and ESE. Such findings can provide effective guidance in understanding and designing high-DBS and high-energy-density ferroelectrics. In addition, the defect concentration has a significant influence on the DBS and the pattern of breakdown paths.