Solid-state Sintering Method Research Articles

Synergistic modulation of SrTiO3-TiO2 colossal permittivity system by internal lattice defects and phase composition: Experimental and theoretical investigations

The SrTiO3–TiO2 composite ceramics with different contents of La doping were fabricated by traditional solid-state sintering methods. The performance of the colossal permittivity ceramics was enhanced by the synergistic design of the internal defect structure and phase composition. When the doping content is 2%, SrTiO3–TiO2 composite ceramics possessed a colossal permittivity (ԑr ∼ 1.1 × 105), low dielectric loss (tanδ ∼ 0.050) and favorable thermal stability (−70 °C-150 °C, ΔC/C25°C ≤ ±15%). Phase structure analysis suggested that a TiO2 secondary phase was induced at the grain boundaries of SrTiO3 phase with the addition of La3+ ions. XPS and dielectric behavior analyses revealed that oxygen vacancies and lattice defects formed by inhomogeneous ion-doping act to modulate the dielectric behavior in ceramics. The IBLC interfacial effects in relation to semiconductor grains and insulation grain boundaries are the main contributors to the colossal permittivity (CP) properties of ceramics, and the contribution of the IBLC effects becomes more prominent with increasing doping content. On the basis of first-principles analysis, the ceramic lattice undergoes severe deformation when the La content is increased, and the gathering of electrons at oxygen vacancies and defects is evident. As a result, it leads to enhanced grain semiconducting properties and interfacial effects, which facilitate colossal permittivity and low dielectric loss for ceramics. The results are prospective in the application of CP ceramics.

Synthesis, Performance Measurement of Dy2EuSbO7/ZnBiDyO4 Heterojunction Composite Catalyst and Photocatalytic Degradation of Chlorpyrifos within Pesticide Wastewater under Visible Light Irradiation

For the first time, a novel catalyst named Dy2EuSbO7 was successfully synthesized via the high-temperature solid-state sintering method (HTSSM). Dy2EuSbO7/ZnBiDyO4 heterojunction photocatalyst (DZHP) was fabricated through the HTSSM for degrading chlorpyrifos (CPS) in the pesticide wastewater under visible light irradiation (VSLID). Under VSLID, DZHP could effectively degrade CPS in pesticide wastewater. The experimental outcomes suggested that the kinetic curve with the Dy2EuSbO7/ZnBiDyO4 heterojunction (DZH) as a photocatalyst for the reduction of CPS under VSLID conformed to the first-order kinetics (FOKT). After VSLID of 156 min, the photocatalytic degradation (PTD) removal rate of CPS using DZH as photocatalyst was 1.12 times, 1.21 times, or 2.96 times that using Dy2EuSbO7 as a photocatalyst, ZnBiDyO4 as a photocatalyst, or nitrogen-doped titanium dioxide as a photocatalyst. After VSLID of 156 min for four cycle degradation tests (FCDTS) with DZH as a photocatalyst, the removal rate of CPS reached 98.78%, 97.66%, 96.59%, and 95.69%, respectively. Above results indicated that the DZHP possessed high stability. Experiments with the addition of trapping agents showed that hydroxyl radicals (•OH) owned the strongest oxidative removal ability for degrading CPS compared with superoxide anions (•O2−) or holes (h+). The oxidation capacity of three oxidation radicals for eliminating CPS was ranked in the ascending order as follows: h+ < •OH < •O2−. Lastly, the possible degradation pathway and degradation mechanism of CPS were discussed in detail. A visible light responsive heterojunction catalyst with high catalytic activity and a photocatalytic reaction system which were capable of efficiently removing toxic organic pollutants from pesticide wastewater were obtained.

Significantly enhanced piezoelectric response in Aurivillius Bi3TiNbO9 ceramics simply by Ce doping

Bi3-xCexTiNbO9 (BTN-100xCe, x = 0, 0.01, 0.03, 0.05, 0.07, 0.09, 0.11) piezoelectric ceramics with ultra-high Curie temperature were fabricated by a solid-state sintering method, and the effect of Ce doping on the structure, dielectric and piezoelectric properties of the ceramics was investigated. All ceramic samples possess a single Aurivillius phase and Ce ions enter both A- and B-sites. Dense microscopic morphology with a remarkable decrease of grain size can be observed due to Ce doping. The resistivity markedly increases after Ce modification, and a significantly enhanced piezoelectric constant d33 of 17.1 pC/N can be achieved in the optimized BTN-7Ce ceramics, which is nearly 6 times that of pure Bi3TiNbO9 (d33 ≈ 3 pC/N). In addition to ultra-high Curie temperature (TC = 886.5 °C) and relatively high resistivity (ρ = 1.2 × 106 Ω cm @ 500 °C), the BTN-7Ce ceramics should be very promising for piezoelectric sensor under the application in high temperature conditions.

Effect of Dy2O3 doping on microstructure and electrical characteristics of ZnO linear resistors

ZnO linear resistors, due to its excellent performance, are widely used in numerous industries and gradually replacing traditional conductive resistors, presenting a broad prospect for application. To study the effects of lanthanide oxides on the microstructure and electrical properties of ZnO-based linear resistors, this paper prepared Dy2O3-doped ZnO-Al2O3-TiO2-NiO based linear resistors using a solid-state sintering method. The results showed that proper doping of Dy2O3 could inhibit the growth of ZnO grains, leading to more uniform grain growth. Additionally, doped with appropriate amount of Dy2O3 could enhance the linear performance of ZnO linear resistors, reduce the grain boundary barrier height (φb), and decrease dielectric loss. Linear resistors with nonlinearity coefficient (α) of 1.07, grain boundary barrier height (φb) of 0.0934 eV and resistance-temperature coefficient (αT) of −5.39 × 10−3/°C were obtained. The doping of Dy2O3 could improve the comprehensive performance of ZnO linear resistors, making the fabricated ZnO linear resistors are more suitable for working in high frequency electric fields. The study and analysis of Dy2O3 doped ZnO linear resistors are of significant importance for the preparation of high performance ZnO linear resistors.

Significantly improved energy storage performance of Na0.5Bi0.5TiO3–BaTiO3 ferroelectric ceramics with a wide temperature range via high-entropy doping

The emergence of high-entropy perovskite materials provides a new research idea to solve the problem of high remnant polarization and low recoverable energy storage density (Wrec) of relaxor ferroelectrics. In this study, barium-based high-entropy perovskite oxides Ba(Zr0.2Sn0.2Hf0.2Nb0.2Ti0.2)O3 (BZSHNT) were introduced into the 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 (BNT-6BT) ceramic by the conventional solid state sintering method. The 0.2BZSHNT doped BNT-6BT ceramic demonstrates significantly improved Wrec of 3.57 J/cm3 and a high efficiency of 81.6 % compared to those of the BNT-6BT ceramic, which is only 0.5 J/cm3 and 60 % respectively. The doped BZSHNT refines the hysteresis loops and drastically reduces the remnant polarization, which lead to the increase of the polarization difference. The 0.8(BNT-6BT)-0.2BZSHNT ceramics show high discharge energy density, good temperature stability (25–200 °C), excellent frequency stability (10–300 Hz) and superior discharge rate (t0.9 = 83 ns) because of its increased TiO6 lattice distortion, atomic disorder, relaxation degree and band gap, as well as the disruption of the long-range ordered ferroelectric domains. Our findings make BNT-6BT doped BZSHNT based ceramics one of the most promising lead-free dielectric energy storage candidates.

Beneficial role of manganese dioxide for reducing surface resistivity to increase surface flashover voltage of vacuum insulating ceramics

Electric vacuum insulated devices generate surface flashover and breakdown under instantaneous high voltage. Flashover voltage can be increased through coating without changing the structure of the ceramic device. Herein, multiphase coatings with different manganese dioxide contents are prepared on α-Al2O3 insulating ceramic surface by screen printing and solid-state sintering methods to yield an average film thickness of about 12.38 μm with good bonding strength. X-ray diffraction shows that the crystal phases of the coating are (Al0.9Cr0.1)2O3 and MnAl2O4. Scanning electron micrographs and atomic force microscopy reveal that greater surface height difference and deeper surface depth are more conducive to increasing the surface roughness and the formation of "pores", and decreasing the surface potential decay rate. When MnO2 content is 0.0069 mol, the deep trap center energy level on the material surface reaches its maximum, increasing from 1.506 eV to 1.550 eV, and the surface resistivity of ceramics decreases from 1016 Ω to 1013 Ω. The formation of deep trap centers on the surface makes it difficult for surface charges to detach, which reduces the charge mobility and surface potential decay rate, and leads to decrease in surface resistivity and increase in surface flashover voltage.

Crystal structures, dielectric properties, and lattice vibrational characteristics of Zn1-xCaxWO4 (x = 0–0.25) composite ceramics

In this work, Zn1-xCaxWO4 (x=0–0.25, ZCWO) composite ceramics were prepared by using the conventional solid-state sintering method at 1070 ℃. The impact of Ca2+ substitution on the lattice vibrational characteristics and dielectric responses of the ZCWO composite ceramics was investigated in detail. The formation of composite ceramics was verified by the Rietveld refined X-ray diffraction data of the ZCWO samples. The lattice vibrational characteristics were also identified and analyzed by the Raman and infrared reflection spectra combined with the theoretical simulations. The vibrational modes analysis of the Raman spectra showed that the internal modes of the ZCWO ceramics correspond to the vibrations of the W-O octahedrons. From the Fourier transform infrared reflectance spectra, the existence of three new vibrational modes of Au (315 cm−1), Au (834 cm−1), and Eu (885 cm−1) at x = 0.15–0.25 was observed, which belong to the modes of the CaWO4 ceramic. In addition, the intrinsic dielectric properties fitted by the four-parameter semiquantum model were in direct agreement with the theoretical values obtained from the Clausius-Mossotti & damping equations and the measured values. Besides, the contribution of each lattice vibrational mode to the intrinsic properties of the ZCWO ceramics was thoroughly studied, which shows that external mode 1 contributes the most to the intrinsic properties. The structure-property relationships of the ZCWO ceramics were established using the Raman modes as a media. The optimum dielectric properties of the ZCWO ceramics were obtained when x = 0.25: εr =13.98 (10.48 GHz), Q × f = 32,188 GHz.

Quaternary piezoelectric ceramics with ultra-high mechanical quality factor

The development of piezoelectric ceramics with large piezoelectric coefficient (d33), high Curie temperature (TC) and high mechanical quality factor (Qm) is still a key challenge for practical application for high-power device. Herein, a novel quaternary piezoelectric ceramics of (0.125-x) Pb0.98Sr0.02(Mg1/3Nb2/3)O3–0.445PbTiO3–0.43PbZrO3-xPb(Mn1/3Nb2/3)O3 (abbreviated as xPMnN-PSMN-PZT) were prepared by the solid-state sintering method. The hard dopant PMnN induced the morphotropic phase boundary (MPB) of PSMN-PZT into a tetragonal-rich region. In addition, the XPS and EPR analysis proved the existence of a large amount of oxygen vacancies (Vo••) in PMnN-PSMN-PZT ceramic system. The composition near tetragonal-rich MPB region and the appearance of defect dipoles formed a strong coupling effect on the domain wall motion and leaded to an ultra Qm value. The optimum piezoelectric properties were achieved at x = 9 mol% with d33 = 260 pC/N, Qm = 3880, tanδ = 0.009 and TC = 332 °C. A significant internal bias field (Ebias) of 8.83 kV/cm was also observed in 0.09PMnN-PSMN-PZT ceramics. The origin of this excellent piezoelectric properties was explained by the phase structure, piezoelectric and dielectric analysis. This work demonstrated a rational strategy to obtain ultra Qm value for high-power piezoceramics.

Microstructure, dielectric, ferroelectric and piezoelectric properties of K0.45Na0.45Li0.1NbO3 lead-free ceramics prepared via cold sintering with post-annealing

Via the method of cold sintering with post-annealing, the lead-free ceramics [Formula: see text][Formula: see text][Formula: see text]NbO3 were prepared. The cold sintered pellet without post-annealing shows a relative density ([Formula: see text] of 77.9%, which is larger than [Formula: see text] of the green pellet via the conventional solid-state sintering (SSS) method ([Formula: see text]). The cold sintered pellets were post-annealed at temperatures between [Formula: see text]C and [Formula: see text]C. The effect of post-annealing temperatures on microstructure, dielectric, ferroelectric and piezoelectric properties of the ceramics was studied in detail. After being post-annealed, the relative densities and grain sizes of the ceramics were increased. The ceramics post-annealed at [Formula: see text]C show excellent dielectric, ferroelectric and piezoelectric properties. Compared to the conventional SSS method, the method of cold sintering with post-annealing is successful in preparing dense [Formula: see text][Formula: see text][Formula: see text]NbO3 lead-free ceramics in a wide temperature range and at relatively low temperatures.

Large electrocaloric effect across the non-hysteretic electrostructural phase transition in lead-free (Ba0.88Ca0.12)(Ti0.94Sn0.06)O3 ceramics

Structural, dielectric, and electrocaloric properties were investigated in Pb-free ceramic (Ba0.88Ca0.12)(Ti0.94Sn0.06)O3 (BCST), synthesized using solid-state sintering method. Rietveld refinement of room temperature XRD data revealed the existence of pure perovskite tetragonal (P4mm) phase. Temperature-dependent XRD analyses confirmed a structural transition from tetragonal to cubic phase near 380 K. Temperature-dependent dielectric constant (εr) and specific heat capacity (Cp) confirmed the presence of thermal hysteresis in two phase transitions near 233 ± 10 K and 254 ± 10 K, and a non-hysteretic behavior at the Curie temperature (TC∼373 ± 10 K). A comprehensive Raman study corroborated the existence of phase transitions. Electrocaloric properties were determined using indirect method utilizing the non-hysteretic nature across TC. A large adiabatic temperature change of |∆T| = 0.52 K, isotropic entropy change |∆S| = 0.68 J/kg.K, electrocaloric coefficients, |∆T/∆E |= 0.311 K.mm/kV and |∆S/∆E| = 0.41 J.mm/K.kg.kV were obtained at 380 K for an electric field of 16.7 kV/cm. Obtained value of |∆T/∆E| is relatively good, reported among other BaTiO3-based ceramics.

(Sb0.5Li0.5)TiO3-Doping Effect and Sintering Condition Tailoring in BaTiO3-Based Ceramics.

(1-x)(Ba0.75Sr0.1Bi0.1)(Ti0.9Zr0.1)O3-x(Sb0.5Li0.5)TiO3 (abbreviated as BSBiTZ-xSLT, x = 0.025, 0.05, 0.075, 0.1) ceramics were prepared via a conventional solid-state sintering method under different sintering temperatures. All BSBiTZ-xSLT ceramics have predominantly perovskite phase structures with the coexistence of tetragonal, rhombohedral and orthogonal phases, and present mainly spherical-like shaped grains relating to a liquid-phase sintering mechanism due to adding SLT and Bi2O3. By adjusting the sintering temperature, all compositions obtain the highest relative density and present densified micro-morphology, and doping SLT tends to promote the growth of grain size and the grain size distribution becomes nonuniform gradually. Due to the addition of heterovalent ions and SLT, typical relaxor ferroelectric characteristic is realized, dielectric performance stability is broadened to ~120 °C with variation less than 10%, and very long and slim hysteresis loops are obtained, which is especially beneficial for energy storage application. All samples show extremely fast discharge performance where the discharge time t0.9 (time for 90% discharge energy density) is less than 160 ns and the largest discharge current occurs at around 30 ns. The 1155 °C sintered BSBiTZ-0.025SLT ceramics exhibit rather large energy storage density, very high energy storage efficiency and excellent pulse charge-discharge performance, providing the possibility to develop novel BT-based dielectric ceramics for pulse energy storage applications.

Microwave dielectric properties and LTCC applications of new glass-free molybdate ceramics Li3Ba2Ln3(MoO4)8 (Ln=Gd, Tm)

The traditional solid-state sintering method was employed to prepare Li3Ba2Ln3(MoO4)8 (Ln = Gd, Tm) ceramics, and the impact of firing temperature on the structure, microstructure and microwave dielectric properties of the novel molybdate Li3Ba2Ln3(MoO4)8 (Ln = Gd, Tm) ceramics was examined. XRD and Rietveld refinement outcomes validate the monoclinic system with the C2/c space group for Li3Ba2Ln3(MoO4)8 (Ln = Gd, Tm). For the Li3Ba2Gd3(MoO4)8 ceramic sintered at 800 °C, a εr is 9.42, a Q × f is 16,988 GHz, and a τf is 4.57 ppm/°C. The Li3Ba2Tm3(MoO4)8 ceramic sintered at 800 °C has a εr of 9.74, a Q × f of 25,401 GHz, and a τf of 1.08 ppm/°C. XRD and EDS analyses prove the good chemical compatibility of the co-sintered Li3Ba2Gd3(MoO4)8 ceramic with the Ag electrode. Therefore, the Li3Ba2Gd3(MoO4)8 ceramic is suitable candidate material for LTCC applications.

Fabrication of Al2O3– Ce:(Y, Tb)3 (Al, Mn)5O12 composite ceramic phosphors for high color rendering white LED/LD illumination

Ce: YAG- Al2O3 composite ceramics are regarded as highly promising materials for laser illumination application due to their high luminous efficacy and thermal stability. Nevertheless, the Ce: YAG ceramics exhibit limited color rendering index (CRI) for indoor lighting due to their low red emission component. In this study, we synthesized high-performance Ce, Mn-doped (Y, Tb)3Al5O12–Al2O3 composite ceramic phosphors via a vacuum solid-state sintering method. It was observed that the introduction of Mn2+ ions created a second luminescence center with an emission peak centered at 580 nm. As the Mn2+ concentration increased, the emission peak redshifted from 580 nm to 591 nm, leading to a significant enhancement in the color rendering index of the ceramics. The cross-energy transfer between Tb3+ and Mn2+, Ce3+ ions augmented the absorption and conversion of blue light by the ceramics, thereby reducing the correlated color temperature greatly. Based on these findings, ceramics with a Ce3+ concentration of 3 at% and a Mn2+ concentration of 4 at% exhibited the highest CRI values (81.3 and 75.6) under both laser excitation and LED excitation, establishing them as strong candidates for achieving high color rendering in white LED/LD illumination applications.

Modified Pb(Mg1/3Nb2/3)O3-PbZrO3-PbTiO3 ceramics with high d33，large Qm and high Tc

The development of piezoelectric ceramics with large piezoelectric coefficient (d33), high Curie temperature (Tc) and high mechanical quality factor (Qm) is still a key challenge for practical application for high-power device. Herein, a series of Sm3+ and Mn2+ ions co-doped 0.15Pb(Mg1/3Nb2/3)O3-(0.85-x)PbZrO3-xPbTiO3 ceramics were prepared by the solid-state sintering method. The optimum piezoelectric properties were achieved at x = 0.435 mol% with a large d33 ∼ 450 pC/N and a high Qm ∼ 1968 near the morphotropic phase boundary (MPB), and with high Tc ∼ 296 °C. The origin of this excellent piezoelectric properties was explained by the phase structure, piezoelectric and dielectric analysis. The composition near MPB region and the appearance of defect dipoles leaded to final excellent piezoelectric properties, and made a harmonization between d33, Tc and Qm. This work demonstrated a rational strategy to obtain large d33, high Tc and high Qm for high-power piezoceramics.

The mechanical properties and chemical durability of granite wastes based glass-ceramics for immobilization of high-level nuclear wastes

In this study, granite wastes based glass-ceramics containing Eu2O3 as simulated radionuclides is successfully synthesized via solid-state sintering method. The structure, mechanical properties and chemical durability are deeply investigated. The main phase in this glass-ceramics is oxyapatite (Ca2Eu8(SiO4)6O2), which is dispersed homogenously in glass matrix. The density dominates the properties of Vickers hardness and bending strength. The glass-ceramics containing 40 wt % of Eu2O3 has the optimal mechanical properties, with the Vickers hardness, bending strength and density of 5.12 GPa, 79.44 MPa and 98.77 %, respectively. The 28 days leaching experiments show that the glass-ceramics containing 40 wt % of Eu2O3 possess excellent chemical durability. The leaching rate of Al3+, Si4+, Fe3+, Ca2+, Eu3+ are 2.3 × 10−4 g m−2 d−1, 6.0 × 10−4 g m−2 d−1, 1.2 × 10−7 g m−2 d−1, 1.4 × 10−4 g m−2 d−1, 3.6 × 10−8 g m−2 d−1, respectively. This study indicates that granite wastes based glass-ceramics have excellent chemical stability and mechanical properties, which provides a novel idea for the immobilization of radioactive wastes.

Evidence of a Large Refrigerant Capacity in Nb-Modified La1.4Sr1.6Mn2−xNbxO7 (0.0 ≤ x ≤ 0.15) Layered Perovskites

In this work, evidence of isothermal magnetic entropy change (∆SM) over a broad temperature region is presented in a series of La1.4Sr1.6Mn2−xNbxO7 Ruddlesden–Popper compounds with niobium modification (Nb) (0.0 ≤ x ≤ 0.15) at the manganese (Mn) site. The ceramic samples were obtained through a solid-state sintering method in optimized conditions. All compounds predominantly possessed Ruddlesden–Popper phase while a few additional reflections were resolved in Nb-doped compounds which indicates the separation of structural phases. These peaks are assigned to a separate layered perovskite and single perovskite with tetragonal symmetry and hexagonal symmetry, respectively. The microstructure of the pure sample reveals uniform grain morphology but in Nb-doped specimens chiefly three types of grains were found. It was assumed that the inter-connected large particles were of R-P phase which is dominant in both parent and x = 0.05 compounds, while the hexagonal and polygonal morphology of grains in higher concentrations of dopants directly corroborates with the symmetry of single perovskite and additional layered perovskite phases, respectively. The parent compound exhibits a single ∆SM curve, whereas all Nb-substituted samples display bifurcated ∆SM curves. This indicated two transition regions with multiple magnetic components, attributed to distinct structural phases. The highest ∆SM values obtained for components corresponding to the R-P phase are 2.32 Jkg−1k−1, 0.75 Jkg−1k−1, 0.58 Jkg−1k−1 and 0.43 Jkg−1k−1 and for the second component located around room temperature are 0.0 Jkg−1k−1, 0.2 Jkg−1k−1, 0.28 Jkg−1k−1 and 0.35 Jkg−1k−1 for x = 0.0, 0.05, 0.10 and 0.15 compositions, respectively, at 2.5 T. Due to the collective participation of both components the ∆SM was expanded through a broad temperature range upon Nb doping.

The effect of dual-sites high-entropy strategy on thermal conductivity of pyrochlore ceramics

The emergence of high-entropy materials has developed a new strategy for the design and optimization of ceramics with desired properties. In this work, the (Gd1/7La1/7Nd1/7Sm1/7Eu1/7Dy1/7Ho1/7)2(Ti1/4Zr1/4Sn1/4Hf1/4)2O7 pyrochlore ceramic with dual-sites high-entropy design has been successfully prepared by a solid-state reaction sintering method. The samples possess a single-phase of pyrochlore structure, and all introduced elements are distributed homogeneously at A and B sites, respectively. Based on the synergistic high-entropy design of A and B sites, the thermal conductivity value of high-entropy pyrochlore ceramic could be diminished to 1.37 W∙m−1∙K−1.

Mechanism of the impact of Ca–Ge co-substitution on the FMR linewidth in BiV-YIG ferrites

Yttrium Iron Garnet (YIG) ferrites, characterized by their superior magnetic and dielectric attributes, are instrumental in advancing the development of microwave devices, particularly in enhancing high-frequency performance, integration, and miniaturization. This paper synthesizes YIG ferrite materials with the composition Bi0.6Y1.4-xCa1+xFe4.5-xV0.5GexO12 (x = 0.10 to 0.50, incrementing by 0.10) through the solid-state sintering method. It delves deeply into the mechanism by which Ca2+-Ge4+ ions substitution regulates the magnetic properties of BiV-YIG. The microstructural and magnetic properties of the samples were systematically tested and analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), vibrating sample magnetometry (VSM), and TE106 perturbation method. At a substitution content of x = 0.50, the substitution of Ge4+ ions for the Fe3+ ions at the d-site transforms the material from ferrimagnetic to paramagnetic, and the saturation magnetization of the sample drops to 132.74 G. By calculating the ferromagnetic resonance (FMR) linewidth using the law of approach to saturation, the study elucidates the negative impact of low saturation magnetization on FMR linewidth. The mechanisms proposed in this paper provide theoretical and experimental bases for reducing the FMR linewidth of high dielectric constant Bi-substituted YIG, paving the way for developing high-dielectric, low-loss YIG ferrite materials for microwave devices.

Structure and Ionic Conductivity of Ga and Nb Dual Doped LLZO Synthesized by Sol-Gel Method

More and more attention has been focused on Li7La3Zr2O12 (LLZO) because of the high ionic conductivity and excellent chemical stability. It is great significance to find suitable dopants for locking cubic LLZO and improving the conductivity of Li+ ions. The uniform nano powder can be obtained by the sol gel synthetic method, which is conducive to maintaining high sintering activity. In this work, Ga and Nb dual doped LLZO solid electrolyte powders were synthesized via sol gel method, and Ga and Nb dual doped LLZO solid electrolyte ceramic were obtained via traditional solid state sintering method. The phase and microstructure of Ga and Nb co-doped LLZO solid electrolyte were analyzed by combine X-ray diffraction with scanning electron microscope. The impedance of Ga and Nb dual doped LLZO (Li6.8-3xGaxLa3Zr1.8Nb0.2O12 (0≤x≤0.3)) solid electrolyte was measured by the electrochemical workstation, and then the conductivity was calculated. The results show that when the doping amount of Ga is x=0.2, it is a pure cubic LLZO structure with the highest conductivity value of 3.7×10-4 S cm-1 (tested at room temperature) due to the sample has a high relative density and reaches the optimal Li+ vacancy concentration.

Reduced Lattice Constant in Al-Doped LiMn2O4 Nanoparticles for Boosted Electrochemical Lithium Extraction.

Extracting lithium selectively and efficiently from brine sources is crucial for addressing energy and environmental challenges. The electrochemical system employing LiMn2O4 (LMO) electrodes has been recognized as an effective method for lithium recovery. However, the lithium selectivity and stability of LMO need further enhancement for its practical applications. Herein, the Al-doped LMO with reduced lattice constant is successfully fabricated through a facile one-step solid-state sintering method, leading to enhanced lithium selectivity. The reduced lattice constant in Al-doped LMO is proved through spectroscopic analyses and theoretic calculations. Compared to the original LMO, the Al-doped LMO (LiAl0.05Mn1.95O4, LMO-Al0.05) exhibits highercapacitance, lower resistance, and improved stability. Moreover, the LMO-Al0.05 with reduced lattice constant can offer higher Li+ diffusion coefficient and lower intercalation energy revealed by cyclic voltammetry and multiscale simulations. When employed in hybrid capacitive deionization (CDI), the LMO-Al0.05 obtains a Li+ intercalation capacity of 21.7mgg-1 and low energy consumption of 2.6Whmol-1 Li+. Importantly, the LMO-Al0.05 achieves a high Li+ extraction percentage (≈86%) with Li+/Na+ and Li+/Mg2+ selectivity of 1653.8 and 434.9, respectively, in synthetic brine. The results demonstrate that the Al-doped LMO with reduced lattice constant could be a sustainable solution for electrochemical lithium extraction.