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1.
《Ceramics International》2015,41(7):8562-8567
The effect of calcination on Li ion conductivity of Li1.5Al0.5Ge1.5(PO4)3 (LAGP) solid electrolyte prepared by a sol–gel method is examined. The Li ion conductivity of LAGP increases with calcination temperature. After reaching maximum conductivity at 850 °C, the conductivity decreases with increase of the calcination temperature. The calcination holding time also strongly affects Li ion conductivity of LAGP. The conductivity increases with holding time until 12 h and then decreases. It is found that the control of crystallization rate is critical to obtain bulk LAGP with high Li ion conductivity. The highest bulk and total conductivities at 30 °C are 9.5×10−4 and 1.8×10−4 S cm−1, respectively, obtained for the bulk LAGP calcined at 850 °C for 12 h.  相似文献   

2.
《Ceramics International》2023,49(6):8718-8724
Recently, LiTa2PO8 (LTPO) has attracted interest as a potential Li-ion solid electrolyte material because of its high bulk ionic conductivity and low grain boundary ionic conductivity. However, most ceramic-based solid electrolytes are fabricated via the high-temperature sintering process (typically above 1000 °C); such temperatures can cause the evaporation of Li from the compound. To replace high-temperature sintering of ceramics, the cold sintering process (CSP) was introduced; this process enables the densification of ceramics and composites at extremely low temperatures (below 300 °C). In this work, we investigate the effect of using the CSP and post annealing on the microstructure and Li-ion conductivity of LTPO pellets. It is found that the CSP pellets have an amorphous phase between particles. This intermediate amorphous phase creates a better contact between particles and is hypothesized to lead to more Li-ion migration paths. The CSP pellet is found to have a high density and high ionic conductivity of (1.19 × 10?5 S/cm). The pellet obtained via the CSP has Li-ion conductivity similar to that of the pellet obtained via dry pressing after it has been annealed. The CSP pellet after post annealing shows good connections between particles and a high Li-ion conductivity of 1.05 × 10?4 S/cm, which is comparable to the conductivity of a pellet obtained via high-temperature sintering. This work provides new evidence that the CSP is a promising alternative to high-temperature sintering for fabricating ceramic solid electrolytes.  相似文献   

3.
《Ceramics International》2020,46(6):7634-7641
In this paper, the microstructure and ionic conductivity of Li1.5Al0.5Ge1.5(PO4)3 (LAGP) solid electrolytes prepared by spark plasma sintering (SPS) were investigated by XRD, SEM, TEM and EIS, respectively. The results showed that as the sintering temperature was increased, both the relative density and the ionic conductivity of the sintered LAGP samples first increased and then decreased, achieving a maximum value of 97% and 2.12 × 10−4 S cm−1 simultaneously at 700 °C. At the same time, the crystallinity of the sintered samples was improved, while a few impurity phases, such as AlPO4 and GeO2, appeared in the samples. It was also found that carbon contamination and oxycarbide gas was be brought in during SPS. Carbon contamination could produce an extra grain boundary impedance to the samples and could be removed by annealing at 500 °C in an air atmosphere. Oxycarbide gas could affect the relative density of the sintered LAGP samples and could be mitigated by choosing a suitable SPS process. Moreover, the shear modulus of the sintered LAGP was measured to be 49.6 GPa, which exceeded the minimum value of 8.5 GPa that was necessary to suppress Li dendrite growth.  相似文献   

4.
NASION-type Li1.5Al0.5Ge1.5(PO4)3(LAGP) is prepared by a novel sol-gel method using low cost inorganic germanium (GeO2) as the precursor. The composition and phase transformation during the heating of the LAGP precursors are analyzed using thermogravimetric-differential scanning calorimetry (TG-DSC) and X-ray diffraction (XRD). The structures and morphologies of the LAGP are characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the LAGP annealed at 900 ℃ is partially crystallized and consists of a large number of nanoscale grains surrounded by amorphous regions. The LAGP particles present an irregular morphology with a large size distribution over a range of 0.2–1 μm. In addition, ionic conductivities of the prepared LAGP first increase and then decrease with an increase in the sintering temperature and time. A high ionic conductivity (4.18 × 10−4Scm-1) with an activation energy of 0.30 eV are obtained for the LAGP sample sintered at 900 °C for 8 h.  相似文献   

5.
To apply SiC ceramics as a matrix for fully ceramic microencapsulated (FCM) fuels, the equivalent boron content (EBC) factors of elements in the sintering additives should be considered as an important criterion. A previously developed quaternary additive composition based on AlN–Y2O3–Sc2O3–MgO contained Sc, which has a relatively high EBC factor (8.56 × 10?3). This study proposes a novel quaternary additive composition (AlN–Y2O3–CeO2–MgO), in which Sc is replaced by Ce (EBC factor = 6.36 × 10-5). The new additive composition achieved successful densification of the SiC matrix at 1850 °C without applied pressure. FCM pellets containing 36 vol% tristructural isotropic (TRISO) particles were successfully sintered at 1850 °C using the above matrix without applied pressure. The thermal conductivities of the FCM pellets prepared via pressureless sintering with 36 vol% TRISO particles were 43.9 W·m-1·K-1 and 25.8 W·m-1·K-1 at 25 °C and 500 °C, respectively.  相似文献   

6.
Oxygen ion conduction in Nd3+‐doped Pb(ZrxTi1?x)O3 (PZT) was investigated by impedance spectroscopy and 18O‐tracer diffusion with subsequent secondary ion mass spectrometry (SIMS) analysis. Ion blocking electrodes lead to a second relaxation feature in impedance spectra at temperatures above 600°C. This allowed analysis of ionic and electronic partial conductivities. Between 600°C and 700°C those are in the same order of magnitude (10?5–10?4 S/cm) though very differently activated (2.4 eV vs. 1.2 eV for ions and electron holes, respectively). Oxygen tracer experiments showed that ion transport mainly takes place along grain boundaries with partly very high local ionic conductivities. Numerical analysis of the tracer profiles, including a near‐surface space charge zone, revealed bulk and grain‐boundary diffusion coefficients. Calculation of an effective ionic conductivity from these diffusion coefficients showed good agreement with conductivity values determined from impedance measurements. Based on these data oxygen vacancy concentrations in grain boundary and bulk could be estimated. Annealing at high temperatures caused a decrease in the grain‐boundary ionic conductivity and onset of additional defect chemical processes near the surface, most probably due to cation diffusion.  相似文献   

7.
The thermal properties were investigated for hot‐pressed zirconium diboride containing solid solution additions of tantalum, molybdenum, rhenium, vanadium, and chromium. The nominal additions were equivalent to 3 at.% of each metal with respect to zirconium. Using 0.5 wt% carbon as a sintering aid, powders were hot‐pressed to near full density at 2150°C. Rietveld refinement of X‐ray diffraction data was used to measure lattice parameters and to ensure that the additives formed solid solutions. Thermal conductivities were calculated from measured thermal diffusivities and temperature‐dependent values for density and heat capacity. Thermal conductivities at 25°C ranged from 88 W·(m·K)?1 for nominally pure ZrB2 down to 28 W·(m·K)?1 for (Zr,Cr)B2. Electron contributions to thermal conductivity were calculated from electrical resistivity measurements using the Wiedemann–Franz law. Decreases in phonon and electron conduction correlated with the size of the metallic additive, indicating that changes in atom size in the Zr lattice positions reduced thermal transport.  相似文献   

8.
The effects of the starting SiC powder (α or β) with the addition of 5.67 wt% AlN–Y2O3–CeO2–MgO additives on the residual porosity and thermal conductivity of fully ceramic microencapsulated (FCM) fuels were investigated. FCM fuels containing ~41 vol% and ~37 vol% tristructural isotropic (TRISO) particles could be sintered at 1870 °C using α-SiC and β-SiC powders, respectively, via a pressureless sintering route. The residual porosities of the SiC matrices in the FCM fuels prepared using the α-SiC and β-SiC powders were 1.1% and 2.3%, respectively. The thermal conductivities of FCM pellets with ~41 vol% and ~37 vol% TRISO particles (prepared using the α-SiC and β-SiC powders, respectively) were 59 and 41 Wm?1K?1, respectively. The lower porosity and higher thermal conductivity of FCM fuels prepared using the α-SiC powder were attributed to the higher sinterability of the α-SiC powder than that of the β-SiC powder.  相似文献   

9.
《Ceramics International》2022,48(10):13531-13540
New innovative approach to fabricate porous alumina ceramics by cold sintering process (CSP) is presented using NaCl as pore forming agent. The effects of CSP and post-annealing temperature on the microstructure and mechanical strength were investigated. Al2O3–NaCl composite with bulk density of 2.92 g/cm3 was compacted firstly using CSP and then a porous structure was formed using post-annealing at 1200°C–1500°C for 30 min. Brazilian test method and Vickers hardness test were used to determine the indirect tensile strength and hardness of the porous alumina, respectively. Meanwhile, the phases and the microstructure were respectively examined using X-ray diffractometer and scanning electron microscope (SEM) complemented by the 3D image analysis with X-ray tomography (XRT). SEM structural and XRT image analysis of cold sintered composite showed a dense structure with NaCl precipitated between Al2O3 particles. The NaCl volatization from the composite was observed during the annealing and then complete porous Al2O3 structure was formed. The porosity decreased from 48 vol% to 28 vol% with the annealing temperature increased from 1200 °C to 1500 °C, while hardness and mechanical strength increased from 14.3 to 115.4 HV and 18.29–132.82 MPa respectively. The BET analysis also showed a complex pore structure of micropores, mesopores and macropores with broad pore size distribution.  相似文献   

10.
Sintering mechanisms and kinetics were investigated for ZrB2 ceramics produced using reaction hot pressing. Specimens were sintered at temperatures ranging from 1800°C to 2100°C for times up to 120 min. ZrB2 was the primary phase, although trace amounts of ZrO2 and C were also detected. Below 2000°C, the densification mechanism was grain‐boundary diffusion with an activation energy of 241 ± 41 kJ/mol. At higher temperatures, the densification mechanism was lattice diffusion with an activation energy of 695 ± 62 kJ/mol. Grain growth exponents were determined to be ~4.5, which indicated that a grain pinning mechanism was active in both temperature regimes. The diffusion coefficients for grain growth were 1.5 × 10?16 cm4/s at 1900°C and 2.1 × 10?15 cm4/s at 2100°C. This study revealed that dense ZrB2 ceramics can be produced by reactive hot pressing in shorter times and at lower temperatures than conventional hot pressing of commercial powders.  相似文献   

11.
Sm0.2Ce0.8O1.9- 30% Na2CO3 (Sm doped ceria (SDC)-30N) nano-composite electrolytes were densified in a single step via cold sintering process (CSP). At 200°C and 450 MPa of uniaxial pressure, samples up to 97% of their theoretical density could be obtained. The effect of processing parameters, such as temperature, uniaxial pressure, processing duration, and moisture content, on the densification of the nano-composite electrolytes was investigated. The thermal, microstructural, and electrical properties of nano-composites were investigated by differential scanning calorimetry, X-ray diffractometer, scanning electron microscope, and EIS analysis. SDC crystallite sizes were found to be around 25 nm, barely coarsened after CSP by which the true nano nature of the nano-composite could be preserved. Because, by conventional processing high density values could not be attained and high processing temperatures in excess of 600°C had to be used, promoting particle coarsening. The highest total electrical conductivity was found to be 2.2 × 10−2 S cm−1 at 600°C, with an activation energy of 0.83 eV for SDC-30N nano-composites. The present investigation revealed that the implementation of cold sintering technique resulted in significant enhancements in the densification of nano-composite electrolytes, thereby rendering them suitable for efficient utilization in SOFC applications, as compared to the conventional production methods.  相似文献   

12.
Lithium ion conductors with garnet‐type structure are promising candidates for applications in all solid‐state lithium ion batteries, because these materials present a high chemical stability against Li metal and a rather high Li+ conductivity (10?3–10?4 S/cm). Producing densified Li‐ion conductors by lowering sintering temperature is an important issue, which can achieve high Li conductivity in garnet oxide by preventing the evaporation of lithium and a good Li‐ion conduction in grain boundary between garnet oxides. In this study, we concentrate on the use of sintering additives to enhance densification and microstructure of Li7La3ZrNbO12 at sintering temperature of 900°C. Glasses in the LiO2‐B2O3‐SiO2‐CaO‐Al2O3 (LBSCA) and BaO‐B2O3‐SiO2‐CaO‐Al2O3 (BBSCA) system with low softening temperature (<700°C) were used to modify the grain‐boundary resistance during sintering process. Lithium compounds with low melting point (<850°C) such as LiF, Li2CO3, and LiOH were also studied to improve the rearrangement of grains during the initial and middle stages of sintering. Among these sintering additives, LBSCA and BBSCA were proved to be better sintering additives at reducing the porosity of the pellets and improving connectivity between the grains. Glass additives produced relative densities of 85–92%, whereas those of lithium compounds were 62–77%. Li7La3ZrNbO12 sintered with 4 wt% of LBSCA at 900°C for 10 h achieved a rather high relative density of 85% and total Li‐ion conductivity of 0.8 × 10?4 S/cm at room temperature (30°C).  相似文献   

13.
The electrical and thermal properties of SiC ceramics containing 1 vol% nitrides (BN, AlN or TiN) were investigated with 2 vol% Y2O3 addition as a sintering additive. The AlN‐added SiC specimen exhibited an electrical resistivity (3.8 × 101 Ω·cm) that is larger by a factor of ~102 compared to that (1.3 × 10?1 Ω·cm) of a baseline specimen sintered with Y2O3 only. On the other hand, BN‐ or TiN‐added SiC specimens exhibited resistivity that is lower than that of the baseline specimen by a factor of 10?1. The addition of 1 vol% BN or AlN led to a decrease in the thermal conductivity of SiC from 178 W/m·K (baseline) to 99 W/m·K or 133 W/m·K, respectively. The electrical resistivity and thermal conductivity of the TiN‐added SiC specimen were 1.6 × 10?2 Ω·cm and 211 W/m·K at room temperature, respectively. The present results suggest that the electrical and thermal properties of SiC ceramics are controllable by adding a small amount of nitrides.  相似文献   

14.
《Ceramics International》2022,48(8):11124-11133
A series of rare-earth-tantalate high-entropy ceramics ((5RE0.2)Ta3O9, where RE = five elements chosen from La, Ce, Nd, Sm, Eu and Gd) were prepared by conventional sintering in air at 1500 °C for 10 h. The (5RE0.2)Ta3O9 high-entropy ceramics exhibit an orthogonal structure and sluggish grain growth. No phase transition occurs in the test temperature of 25–1200 °C. The thermal conductivities of all (5RE0.2)Ta3O9 ceramics are in the range of 1.14–1.98 W m?1 K?1 at a test temperature of 25–500 °C, approximately half of that of YSZ. The sample of (Gd0.2Ce0.2Nd0.2Sm0.2Eu0.2)Ta3O9 exhibits a low glass-like thermal conductivity with a value of 1.14 W m?1 K?1 at 25 °C. The thermal expansion coefficient of (5RE0.2)Ta3O9 ceramics ranges from 5.6 × 10?6 to 7.8 × 10?6 K?1 at 25–800 °C, and their fracture toughness is high (3.09–6.78 MPa·m1/2). The results above show that (5RE0.2)Ta3O9 ceramics could be a promising candidate for thermal barrier coatings.  相似文献   

15.
B4C-TiB2 composites were contaminated with WC to study the effect on densification, microstructure and properties. WC was introduced through a mild or a high energy milling with WC-6?wt%Co spheres or directly as sintering aid to 50?vol% B4C / 50?vol%TiB2 mixtures. High energy milling was very effective in improving the densification thanks to the synergistic action of WC impurities, acting as sintering aid, and size reduction of the starting TiB2-B4C powders. As a result, the sintering temperature necessary for full densification decreased to 1860?°C and both strength and hardness benefited from the microstructure refinement, 860?±?40 MPa and 28.5?±?1.4?GPa respectively. High energy milling was then adopted for producing 75?vol% B4C/25?vol% TiB2 and 25?vol% B4C/ 75vol%TiB2 mixtures. The B4C-rich composition showed the highest hardness, 32.2?±?1.8?GPa, whilst the TiB2-rich composition showed the highest value of toughness, 5.1?±?0.1?MPa?m0.5.  相似文献   

16.
Cold sintering process (CSP) is an extremely low‐temperature sintering process (room temperature to ~200°C) that uses aqueous‐based solutions as transient solvents to aid densification by a nonequilibrium dissolution‐precipitation process. In this work, CSP is introduced to fabricate microwave and packaging dielectric substrates, including ceramics (bulk monolithic substrates and multilayers) and ceramic‐polymer composites. Some dielectric materials, namely Li2MoO4, Na2Mo2O7, K2Mo2O7, and (LiBi)0.5MoO4 ceramics, and also (1?x)Li2MoO4?xPTFE and (1?x)(LiBi)0.5MoO4?xPTFE composites, are selected to demonstrate the feasibility of CSP in microwave and packaging substrate applications. Selected dielectric ceramics and composites with high densities (88%‐95%) and good microwave dielectric properties (permittivity, 5.6‐37.1; × f, 1700‐30 500 GHz) were obtained by CSP at 120°C. CSP can be also used to potentially develop a new co‐fired ceramic technology, namely CSCC. Li2MoO4?Ag multilayer co‐fired ceramic structures were successfully fabricated without obvious delamination, warping, or interdiffusion. Numerous materials with different dielectric properties can be densified by CSP, indicating that CSP provides a simple, effective, and energy‐saving strategy for the ceramic packaging and microwave device development.  相似文献   

17.
《Ceramics International》2022,48(18):25949-25957
The design and regulation of the ion transport channels in the polymer electrolyte is an important means to improve the lithium ion transport behavior of the electrolyte. In this work, we for the first time combined the high ionic conductive inorganic ceramic electrolyte Li1.5Al0.5Ge1.5(PO4)3 (LAGP) with flexible polypropylene oxide (PPO) polymer electrolyte to synthesize a high-filling LAGP/PPO composite solid electrolyte film and regulated the ion transport channels from ‘Ceramics-in-Polymer’ mode to ‘Polymer-in-Ceramics' mode by optimizing the ratio of LAGP vs. PPO. The results reveal that when the LAGP content <40%, the electrolyte belongs to ‘LAGP-in-PPO’, and then changes to ‘PPO-in-LAGP’ when the LAGP content exceeds 40%. Compared with ‘LAGP-in-PPO’, the ‘PPO-in-LAGP’ shows better comprehensive properties, especially for the 75% LAGP-filled PPO electrolyte, the room-temperature ionic conductivity is as high as 3.46 × 10?4 Scm?1, the ion migration number and voltage stable window reach 0.83 and 4.78 V respectively. This high-filled composite electrolyte possesses high tensile stress of 40 MPa with a strain of 46% and withstands working environment up to 200 °C. The NCM622/Li solid-state battery composed of this electrolyte also presents good rate and cycle performances with a capacity retention of 80% after 230 cycles at 0.3C because of its high ion transport capability and good inhibition of lithium dendrites. This composite structural design is expected to develop high-performance solid-state electrolytes suitable for high-voltage solid-state lithium batteries.  相似文献   

18.
MoSi2‐ and WSi2‐based electroconductive ceramic composites were fabricated using 40‐80 vol% fine‐ and coarse‐Al2O3, and ZrO2 particles (refractory oxides) after sintering in argon. Their chemical and thermal stability was tested between 1400°C‐1600°C for up to 48 hours. X‐ray diffraction analysis showed the formation of secondary 5‐3 metal silicide (Mo5Si3, W5Si3) and silica phases on the grain boundaries and surface. The fraction of the W5Si3 (11.4‐38.8 vol%) was significantly higher than that of the Mo5Si3 (3.3‐7.3 vol%) in the composites after annealing at 1400°C for 48 hours. The rates of grain growth in the composites (0.013‐0.023 μm/h) were highly decreased by a grain‐boundary pinning effect. This effect was relatively better with the addition of the coarse‐grained oxides due to their more homogeneous distribution throughout the microstructure. The 20–80 vol% MoSi2‐Al2O3 (fine‐grained) composite exhibited an electrical conductivity of 8.8 S/cm at 900°C. At the 60 vol% silicide content, MoSi2–Al2O3 (coarse‐grained) and WSi2–Al2O3 (fine‐grained) showed higher electrical conductivity (126‐128 S/cm) at 900°C. The density, porosity level, particle distribution, intrinsic conductivity of silicide phase, particle size, and fraction of the secondary 5‐3 silicide phase highly influenced their electrical properties.  相似文献   

19.
The effects of Li2O–ZnO–B2O3 (LZB) glass addition on densification and dielectric properties of Ba4(Nd0.85Bi0.15)9.33Ti18O54 (BNBT) have been investigated. At a given ratio of ZnO/B2O3, the glass softening point decreases, but the thermal expansion coefficient and dielectric constant increase with increasing Li2O content in the LZB glass. With 10 vol% LZB glass, the densification temperature reduces greatly from 1300°C for pure BNBT to 875°C–900°C for BNBT + LZB dielectric, and the densification enhancement becomes more significant with increasing Li2O content in the LZB glass. The above result is attributed to a chemical reaction taking place at the interface of LZB/BNBT during firing, which becomes less extensive with increasing Li2O content in the LZB glass. Therefore, more residual LZB glass, which acts as a densification promoter to BNBT, is left with increasing Li2O content. For the LZB glass with a Li2O content in the range 10–30 mol%, the resulting 90 vol% BNBT + 10 vol% LZB microwave dielectric has a dielectric constant of 55–70, product (Q × fr) of quality factor (Q) and resonant frequency (fr) of 1000–3000 GHz at 5–5.79 GHz, and a temperature coefficient of resonant frequency (τf) of 10–60 ppm/°C in the temperature range between 25°C and 80°C.  相似文献   

20.
The influence of indium doping on chemical stability, sinterability, and electrical properties of BaCe0.5Zr0.3Y0.2O3‐δ was investigated. The phase purity and the chemical stability of the powders in humid pure CO2 were evaluated by XRD. The dense electrolyte pellets were formed after the calcination at 1450°C for 8 h. SEM images and shrinkage plot showed that the sinterability of the samples was apparently improved by doping indium. The electrical conductivity was measured by impedance test through two‐point method, at both low (200–350°C) and high temperature ranges (450–850°C) in different atmospheres. BaCe0.4Zr0.3In0.1Y0.2O3‐δ has been proved to be the optimal composition which simultaneously maximized the chemical stability, sinterability, and electrical conductivity which reached 1.1 × 10?2 S/cm in wet hydrogen at 700°C, comparing with the 1.3 × 10?2 S/cm for original BaCe0.5Zr0.3Y0.2O3‐δ. Anode support fuel cell with a thin BaCe0.4Zr0.3In0.1Y0.2O3‐δ electrolyte (15 μm) was fabricated by spin coating method. Maximum power density of 0.651 W/cm2 was obtained when operating at 700°C and fed by humid H2 (containing H2O 3 vol%). The obtained fuel cell could efficiently run at 650°C for more than 100 h without any attenuation.  相似文献   

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