New Li solid electrolytes

New Li-ion conductors with several different structure types are reported. Li₄B₇O₁₂(Cl,Br) and LiM₂P₃O₁₂ (MZr, Hf) have framework structures. The others are based on structures with isolated polyhedra in a network of edge-linked Li polyhedra and include Li_2+xC_1?xB_xO₃, Li_3?x B_1?xC_xO₃, Li_4+xSi_1?xSi_1?xAl_xO₄, Li_4?xSi_1?xP_xO₄, Li_4?2xSi_1?xS_xO₄ and Li _5?xAl_1?xSi_xO₄. Li_0.8Zr_1.8 Ta_0.2P₃O₁₂ has the best room temperature conductivity, ～5 × 10^?6 (Ωcm)_?1. At 300°C, the conductivities of Li_3.75Si_0.75P_0.25O₄, Li_3.4Si_0.3O₄ and Li_2.25C_0.75B_0.25O₃ are 1 × 10^?2 (Ωcm)^?1. These compositions resist attack by molten li at 200°C and some can be easily prepared as dense ceramics.     

Microwave Processing for Improved Ionic Conductivity in Li2O–Al2O3–TiO2–P2O5 Glass‐Ceramics

Li_1.4Al_0.4Ti_1.6(PO₄)₃ (LATP) was synthesized using a glass‐ceramics approach through crystallization in a conventional box furnace and a modified microwave furnace. The microstructure of samples that were microwave processed at 1000°C showed a larger average grain size (0.87 μm) when compared with the grain size of conventionally processed samples (0.30 μm) at the same temperature. Microwave processing led to significant enhancement of the conductivity when compared with conventional processing for all crystallization temperatures investigated. The highest total conductivity achieved was of glass microwave processed at 1000°C, with a conductivity of 5.33 × 10^?4 S/cm. This conductivity was five times higher than that of LATP crystallized conventionally at the same temperature.     

Correlation between grain size and electrical properties of high-temperature lead-free 0.70BiFeO3-0.30BaTiO3 ceramics

0.70BiFeO₃-0.30BaTiO₃ (0.70BF-0.30BT) ceramics have been widely concerned because of their potential applications for high-temperature piezoelectric devices. In this work, a series of dense 0.70BF-0.30BT ceramics with average grain size variation from 0.55 to 6.0 μm were prepared. XRD results indicate that 0.70BF-0.30BT ceramics show the coexistence of rhombohedral and pseudo-cubic phases and the volume fraction of the rhombohedral phase increase with the grain size. The dielectric, ferroelectric and piezoelectric properties increase with the grain size initially from 0.55 to 5.0 μm and then decrease slightly. Values of d₃₃, P_r, and ε_r, of 0.70BF-0.30BT ceramics with the grain size of 5.0 μm are 185 pC/N, 21.2 μC/cm², and 638, respectively, about five times higher than those ceramics with fine-grain of 0.55 μm. Of particular importance is that 0.70BF-0.30BT ceramics with large grain sizes possess better piezoelectric thermal stability due to the much stabler poled domain state with the rising temperature. The detailed structural studies indicate that the enhanced electric properties are owing to the significantly improved domain motion and the increased lattice distortion. This clarifying the relationship between electrical properties and grain size offers a novel way of improving the performances of piezoceramics.     

Accurate Exploration of the Intrinsic Lattice Thermal Conductivity of Si2N2O by Combined Theoretical and Experimental Investigations

Si₂N₂O is a promising ceramic with various structural and functional applications. Precisely exploring its thermal conductivity is crucially important to evaluate its thermal transport reliability as high‐temperature structural component and electronic device. In this paper, temperature‐dependent lattice thermal conductivity of Si₂N₂O is studied based on a method integrating density functional theory calculations and experimental measurements. The relationship between the complex crystal structure (or heterogeneous chemical bonding) and lattice thermal conductivity of Si₂N₂O is studied. We herein show that Si₂N₂O intrinsically has moderately high lattice thermal conductivity [30.9 W·(m·K)^?1 at 373 K], but extrinsic phonon scattering mechanisms, such as phonon scattering by point defects and grain boundaries etc., might significantly degrade the magnitude in experimental measurement [15.0 W·(m·K)^?1 at 373 K]. This work suggests the significance that understanding the intrinsic thermal conductivity, namely the upper limit value, is a precursor to deciphering the more complicated heat transport behavior of Si₂N₂O.     

Influence of doping with various cations on electrical conductivity of apatite-type neodymium silicates

Apatite-type neodymium silicates doped with various cations at the Si site, Nd₁₀Si₅BO_27?δ (B=Mg, Al, Fe, Si), were synthesized via the high-temperature solid state reaction process. X-ray diffraction and complex impedance analysis were used to investigate the microstructure and electrical properties of Nd₁₀Si₅BO_27?δ ceramics. All Nd₁₀Si₅BO_27?δ ceramics consist of a hexagonal apatite structure with a space group P63/m and a small amount of second phase Nd₂SiO₅. Neodymium silicates doped with Mg²⁺ or Al³⁺ cations at the Si site have an enhanced total conductivity as contrasted with undoped Nd₁₀Si₆O₂₇ ceramic at all temperature levels. However, doping with Fe³⁺ cations at the Si site has a little effect on improving the total conductivity above 873 K. The enhanced oxide-ion conductivity in a hexagonal apatite-type structure depends upon the diffusion of interstitial oxide-ion through oxygen vacancies induced by the Mg²⁺ or Al³⁺ substitution to the Si⁴⁺ site and through the channels between the SiO₄ tetrahedron and Nd³⁺ cations. At 773 K, the highest total conductivity is 4.19×10^?5 S cm^?1 for Nd₁₀Si₅MgO₂₆ ceramic. At 1073 K, Nd₁₀Si₅AlO_26.5 silicate has a total conductivity of 1.55×10^?3 S cm^?1, which is two orders of magnitude higher than that of undoped Nd₁₀Si₆O₂₇.     

Controllable microstructure tailoring for regulating conductivity in Al-doped ZnO ceramics

Structural and electrical behavior of Al₂O₃ doped ZnO-based ceramics were investigated as function of the aluminum doping ratios under reducing sintering atmosphere (N₂+CO). With Al₂O₃ doping from 0.1 mol% to 0.55 mol%, the electrical conductivity increases firstly to a maximum (1.52 × 10⁵ S·m⁻¹) at 0.25 mol%, and then decreases gradually. The increased conductivity is explained by the formation of shallow donors as Al_Zn-Zn_i complexes with doping to 0.25 mol%. As Al₂O₃ doping further increasing to 0.55 mol%, ZnAl₂O₄ spinel phase and more ZnO-ZnO grain boundaries are formed, hindering charge carriers transport, to decrease charge carrier mobility, thus to decrease the conductivity of ZnO ceramics. Therefore, the Al_Zn-Zn_i complexes, grain boundaries and ZnAl₂O₄ spinel can be adjusted by doping different Al₂O₃ amount, thus the carriers’ concentration and their mobility are optimized to increase the conductivity. Our work, as a fundamental research, is of great significance to control conductivity by regulating Al₂O₃ doping.     

0.73ZrTi2O6–0.27MgNb2O6 microwave dielectric ceramics modified by Al2O3 addition

0.73ZrTi₂O₆–0.27MgNb₂O₆ ceramics with various Al₂O₃ contents (0‐2.0 wt%) were prepared by conventional ceramic route. The effects of Al₂O₃ on the phase composition, microstructure, conductivity, and microwave dielectric properties were systematically investigated. The coexistence of a disordered α–PbO₂‐type phase and a rutile second phase was found in all compact ceramics with low Al₂O₃ contents (x = 0, 0.5, and 1.0 wt%), while a corundum phase was detected when Al₂O₃ additive increased to 1.5 and 2.0 wt% based on X‐ray diffraction results. With the addition of Al₂O₃, the decreased grain size of the matrix phase was observed using field‐emission scanning electron microscope, accompanied with increased resistivity and band‐gap energy. Additionally, Al₂O₃ additives efficiently improved the quality factor of the ceramics. After sintering at 1360°C for 3 hours, the ceramic with 1.0 wt% Al₂O₃ exhibited excellent microwave dielectric properties: a dielectric constant of 43.8, a quality factor of 33 900 GHz (at 6.6 GHz), and a near‐zero temperature coefficient of resonant frequency (3.1 ppm/^°C).     

Phase transformation and grain-boundary segregation in Al-Doped Li7La3Zr2O12 ceramics

Cubic phase garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is a promising solid electrolyte for highly safe Li-ion batteries. Al-doped LLZO (Al-LLZO) has been widely studied due to the low cost of Al₂O₃. The reported ionic conductivities were variable due to the complicated Al³⁺-Li⁺ substitution and Li_xAlO_y segregation in Al-LLZO ceramics. This work prepared Li_7?3xAl_xLa₃Zr₂O₁₂ (x = 0.00~0.40) ceramics via a conventional solid-state reaction method. The AC impedance and corresponding distribution of relaxation times (DRT) were analyzed combined with phase transformation, cross-sectional microstructure evolution, and grain boundary element mapping results for these Al-LLZO ceramics to understand the various ionic transportation levels in LLZO with different Al-doping amounts. The low conductivity in low Al-doped (0.12~0.28) LLZO originates from the slow Li⁺ ion migration (1.4~0.25 μs) in the cubic-tetragonal mixed phase. On the other hand, LiAlO₂ and LaAlO₃ segregation occur at the grain boundaries of high Al-doped (0.40) LLZO, resulting in a gradual Li⁺ ion jump (6.5 μs) over grain boundaries and low ionic conductivity. The Li_6.04Al_0.32La₃Zr₂O₁₂ ceramic delivers the optimum Li⁺ ion conductivity of 1.7 × 10^?4 S cm^?1 at 25 °C.     

Dielectric properties of Si3N4–SiCN composite ceramics in X-band

Si₃N₄–SiCN composite ceramics were successfully fabricated through precursor infiltration pyrolysis (PIP) method using polysilazane as precursor and porous Si₃N₄ as preform. After annealed at temperatures varying from 900 °C to 1400 °C, the phase composition of SiCN ceramics, electrical conductivity and dielectric properties of Si₃N₄–SiCN composite ceramics over the frequency range of 8.2–12.4 GHz (X-band) were investigated. With the increase of annealing temperature, the content of amorphous SiCN decreases and that of N-doped SiC nano-crystals increases, which leads to the increase of electrical conductivity. After annealed at 1400 °C, the average real and imaginary permittivities of Si₃N₄–SiCN composite ceramics are increased from 3.7 and 4.68 × 10^?3 to 8.9 and 1.8, respectively. The permittivities of Si₃N₄–SiCN composite ceramics show a typical ternary polarization relaxation, which are ascribed to the electric dipole and grain boundary relaxation of N-doped SiC nano-crystals, and dielectric polarization relaxation of the in situ formed graphite. The Si₃N₄–SiCN composite ceramics exhibit a promising prospect as microwave absorbing materials.     

Li ion conduction of perovskite Li0.375Sr0.4375Ti0.25Ta0.75O3 and related compounds

In this work, perovskite-structured Li_0.375Sr_0.4375M_0.25N_0.75O₃ (M=Ti, Sn, N=Nb, Ta) solid electrolytes were synthesized by conventional solid state reaction method. Phase compositions, fractured morphologies and conductivities of these compounds were investigated by X-ray diffraction, scanning electron microscope and AC-impedance spectroscopy, respectively. X-ray diffraction analysis confirms that all of Li_0.375Sr_0.4375M_0.25N_0.75O₃ (M=Ti, Sn, N=Nb, Ta) ceramics present perovskite structure. Pure Li_0.375Sr_0.4375Ti_0.25Ta_0.75O₃ and Li_0.375Sr_0.4375Sn_0.25Ta_0.75O₃ perovskite ceramics were obtained. But impurities were detected in Li_0.375Sr_0.4375Ti_0.25Nb_0.75O₃ and Li_0.375Sr_0.4375Sn_0.25Nb_0.75O₃. Among all investigated compounds, Li_0.375Sr_0.4375Ti_0.25Ta_0.75O₃ shows the highest total ionic conductivity of 2.60 × 10^?4 S cm^?1 at room temperature and the lowest activation energy of 0.347 eV. Conductivities of Li_0.375Sr_0.4375Sn_0.25Ta_0.75O₃ and Li_0.375Sr_0.4375Sn_0.25Nb_0.75O₃ were 4.4 × 10^?5 S cm^?1 and 1.82 × 10^?6 S cm^?1, respectively. Their conductivities were much lower than Li_0.375Sr_0.4375Ti_0.25Ta_0.75O₃ and Li_0.375Sr_0.4375Ti_0.25Nb_0.75O₃.     

Structural,optical, electrical and dielectric properties of (Sr1-xMgx)(Sn0.5Ti0.5)O3 (X=0.00, 0.25, 0.50, 0.75) ceramics via solid state route

We have prepared (Sr_1-xMg_x)(Sn_0.5Ti_0.5)O₃, (X = 0.00, 0.25, 0.50, 0.75) samples by the solid state reaction method and studied the structural, optical, electrical modulus and the other dielectric properties of the samples with respect to variation in frequencies (1 × 10⁹ to 2 × 10⁹ Hz) using Impedance Analyzer. This study suggests that the XRD patterns of the samples have shown that this possesses cubic perovskite structure in space group Pm-3m and scanning electron microscope was used to analyze the grain size distribution and porosity of the ceramic. The dielectric properties of these materials were strongly dependent upon on concentration X as well as amount of frequencies. The existence of metal oxygen bonds of Sr–Ti–O was verified by Fourier Transform Infra Red (FTIR) spectrum at 540 cm⁻¹. The highest PL intensity of 716.38 that exhibits the green emission (508.5 nm) was obtained for the composition of (Sr_0.25Mg_0.75)(Sn_0.5Ti_0.5)O₃. AC conductivity slowly decreases with increasing Mg substitution and also the sample (Sr_0.25Mg_0.75)(Sn_0.5Ti_0.5)O₃ having the lowest (constant) value of conductivity at 1 GHz–2GHz.     

Structure and thermal properties of Al2O3-doped Gd3TaO7 as potential thermal barrier coating

In this paper, a series of solid solutions ceramics of (Al_xGd_1-x)₃TaO₇ (x = 0, 0.01, 0.03, 0.05) were synthesized via solid-state reaction. X-ray diffraction (XRD) and Raman spectroscopy analysis indicated that the crystal structure of (Al_xGd_1-x)₃TaO₇ ceramics is weberite in spite of the content of Al³⁺ is up to 5 mol.%. The thermal conductivities of (Al_xGd_1-x)₃TaO₇ ceramics range from 1.37 W?m^?1 K^?1 to 1.47 W?m^?1 K^?1 at 900 ℃, which is much lower than that of 7–8 YSZ (about 2.5 W?m^?1 K^?1). The thermal expansion coefficients (TECs) of (Al_xGd_1-x)₃TaO₇ ceramics vary in the range of 6–10 × 10^-6 K^-1 within the temperature range 100–1200 ℃, and the values are close to the TECs of 7–8 YSZ. Given the low thermal conductivity and high thermal expansion coefficients of (Al_xGd_1-x)₃TaO₇ ceramics, they have the potential to be the next generational thermal barrier coating materials.     

Enhanced transduction coefficient and thermal stability of 0.75BiFeO3-0.25BaTiO3 ceramics for high temperature piezoelectric energy harvesters applications

Owing to the coexistence of high depolarization temperature of 500 °C and good piezoelectric properties, 0.75BiFeO₃-0.25BaTiO₃-0.5mol%MnO₂ (BFBTMn) ceramics show potential energy harvesting applications at elevated temperature. Chemical modifications are usually difficult to improve transduction coefficient (d₃₃×g₃₃) due to the opposite directions of d₃₃ and g₃₃. Herein, the BFBTMn ceramic powders with different average grain sizes of 500 (S₁), 700 (S₂) and 800 (S₃) nm were mixed together for ceramics preparation. This method promotes the grain size, relative density and rhombohedral phase volume fraction of BFBTMn ceramics, leading to the much improved piezoelectric transduction coefficient and its thermal stability. The transduction coefficient of ceramics with optimized weight ratio (1S₁:2S₂:1S₃) reaches up to 4644 × 10^?15 m²/N, about 51% higher than those without mixed powder and at least 60% higher than those reported in the literatures, while its degradation from room temperature to 500 °C is about 15%, much smaller than that (30%) of ceramics without mixed powders. These investigations pave a new way to tailor the transduction coefficient and its thermal stability of BF-BT piezoelectric ceramics for high temperature energy harvesting devices.     

Effect of MgO/Al2O3 ratio on the crystallization behaviour of Li2O–MgO–Al2O3–SiO2 glass-ceramic and its wettability on Si3N4 ceramic

The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li₂O–MgO–Al₂O₃–SiO₂ glass-ceramic for the application of joining Si₃N₄ ceramics. We investigated the influence of the MgO/Al₂O₃ composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi₂O₆ and Mg₂SiO₄ were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg₂SiO₄. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10^?6/°C, which was very close to that of Si₃N₄ ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si₃N₄ ceramic surface was 32° and the interface was well bonded.     

The role of Ca2+ ions in the formation of high optical quality Cr4+,Ca:YAG ceramics

The distribution of Ca²⁺ ions in high optical quality Cr⁴⁺,Ca:YAG ceramics after vacuum sintering followed by air annealing was successfully investigated by HRTEM, STEM, EDX, XPS and optical absorption spectroscopy. The HRTEM microscopy reveals the formation of clear grain boundaries without any impurity phase. A highly-doped thin Ca-rich layer was detected at the grain boundary with Ca²⁺ concentration up to 4.9% RTM, while the concentration of Ca²⁺ ions in the grain volume is less than 0.25%. The layer suppressed grain growth allowing the production of high optical quality ceramics with the average grain size of 1.95 ± 0.27 μm, which is five times smaller than in calcium-free ceramics.The air annealing of Cr⁴⁺,Ca:YAG ceramics results in a 10-fold decrease in Ca²⁺ ion concentration at the grain boundaries, practically removing the Ca-rich layer, moreover, the procedure generates Cr⁴⁺ ions within the grains. Most of the calcium originated from the Ca-rich layer diffuses outside the ceramics or dissolves into Al₂O₃ impurities without interfering with the generation of Cr⁴⁺.     

Effect of a new nonoxide additive,Y3Si2C2, on the thermal conductivity and mechanical properties of Si3N4 ceramics

Enhancement of the thermal conductivity of silicon nitride is usually achieved by sacrificing its mechanical properties (bending strength). In this study, β-Si₃N₄ ceramics were prepared using self-synthesized Y₃Si₂C₂ and MgO as sintering additives. It was found that the thermal conductivity of the Si₃N₄ ceramics was remarkably improved without sacrificing their mechanical properties. The microstructure and properties of the Si₃N₄ ceramics were analyzed and compared with those of the Y₂O₃-MgO additives. The addition of Y₃Si₂C₂ eliminated the inherent SiO₂ and introduced nitrogen to increase the N/O ratio of the grain-boundary phase, inducing Si₃N₄ grain growth, increasing Si₃N₄ grain contiguity, and reducing lattice oxygen content in Si₃N₄. Therefore, by replacing Y₂O₃ with Y₃Si₂C₂, the thermal conductivity of the Si₃N₄ ceramics was significantly increased by 31.5% from 85 to 111.8Wm⁻¹K⁻¹, but the bending strength only slightly decreased from 704 ± 63MPa to 669 ± 33MPa.     

Synthesis,microstructure and property characterization of Mo4Y2Al3B6 ceramic fabricated by spark plasma sintering

Polycrystalline Mo₄Y₂Al₃B₆ ceramic (92.84 wt% Mo₄Y₂Al₃B₆ and 7.16 wt% MoB) was prepared by spark plasma sintering at 1250 ℃ under 30 MPa using Mo, Y, Al, and B as starting materials. The dense sample obtained has a high relative density of 96.6 %. The average thermal expansion coefficient is 8.38 × 10^?6 K^?1 in the range of 25–1000 ℃. The thermal diffusivity decreases from 6.50 mm²/s at 25 °C to 4.33 mm²/s at 800 °C. The heat capacity, thermal conductivity, and electrical conductivity are 0.30 J·g^?1·K^?1, 11.73 W·m^?1·K^?1, and 0.66 × 10⁶ Ω^?1·m^?1 at 25 °C, respectively. Vickers hardness with increasing load in the range of 10–300 N at room temperature decreases from 10.82 to 9.49 GPa, and the fracture toughness, compressive strength, and flexural strength are 5.14 MPa·m^1/2, 1255.14 MPa, and 384.82 MPa, respectively, showing the promising applications as structural-functional ceramics.     

High Electric‐Induced Strain and Temperature‐Dependent Piezoelectric Properties of 0.75BF–0.25BZT Lead‐Free Ceramics

0.75BiFeO₃–0.25Ba(Zr_xTi_1?x) + 0.6 wt% MnO₂ (0.75BF–0.25BZT) ceramics with Mn addition were prepared by the solid‐state reaction method. The high‐field strain and high‐temperature piezoelectric properties of 0.75BF–0.25BZT ceramics were studied. Introduction of Zr in the solid solutions decreased the Curie temperature slightly, and improved the dielectric and piezoelectric properties obviously. The piezoelectric properties of 0.75BZT–0.25BT ceramics reached the maximum at Zr content of 10 mol%. The Curie temperature T_c, dielectric constant ε and loss tanδ (1 kHz), piezoelectric constant d₃₃, and planner electromechanical coupling factor k_p of 0.75BF–0.25BZT ceramics with 10 mol% Zr were 456°C, 650, 5%, 138 pC/N, and 0.30, respectively. The high‐field bipolar and unipolar strain under an electric field of 100 kV/cm reached up to 0.55% and 0.265%, respectively, which were comparable to those of BiScO₃–PbTiO₃ and “soft” PZT‐based ceramics. The typical “butterfly”‐shaped bipolar strain and frequency‐dependent peak‐to‐peak strain indicated that the large high‐field‐induced strain may be due to non‐180° domain switching. Rayleigh analysis reflected that the improved piezoelectric properties resulted from the enhanced extrinsic contribution by Zr doping. The unipolar strain of 0.75BF‐0.25BZT ceramics with 10 mol% Zr was almost linear from RT to 200°C. These results indicated that 0.75BF–0.25BZT ceramics were promising candidates for high‐temperature and lead‐free piezoelectric actuators.     

Tribological behavior of ceramic materials (Si3N4, SiC and Al2O3) in aqueous medium

The friction and wear behavior of self-mated Si₃N₄, SiC and Al₂O₃ in water were investigated by varying the test conditions of applied load and sliding speed. It was found that, for self-mated Si₃N₄ and SiC ceramics, the tribochemical reaction resulted in surface smoothening with low friction coefficient at high load and high speed condition. Al₂O₃ shows high friction coefficient, but better wear rate (10⁻¹¹ mm²/N) than other ceramic materials.     

Enhanced “overall” ionic conductivity in Li1+xAlxTi2−x(PO4)3 (0.3 ≤ x ≤ 0.7) ceramics prepared from sol-gel powders by spark plasma sintering

The Li_1+xAl_xTi_2?x(PO₄)₃ (LATPx) series displays the highest “bulk” reported conductivity, but a much lower “overall” contribution, that changes with the powder preparation and sintering conditions. In this work, the preparation of LATPx ceramics is discussed, by using the sol-gel technique for powders synthesis and mild spark plasma (SPS) for ceramics sintering at 800 °C. An “overall” conductivity ~ 2.10^?3 Ω^?1 cm^?1 was obtained for the x = 0.4 composition, that was the result of a high “bulk” conductivity, an optimized microstructure and almost full density, in absence of micro-cracks, with a small content of secondary phases and clean grain boundaries. Fast-ion ceramics prepared by SPS are good candidates for solid electrolytes in all solid state batteries (ASSB).