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At least 523 records · Page 29

Polymer–Ceramic Composite Electrolytes for Lithium Batteries: A Comparison between the Single-Ion-Conducting Polymer Matrix and Its Counterpart

Single-ion-conducting polymer electrolytes are attractive to use in lithium batteries as the transference number of the lithium cation approaches unity. This helps prevent concentration gradients across the electrolyte, which can result in dendrite formation. The addition of ceramic particles to polymer electrolytes at high loadings can increase the mechanical strength of the polymer, which can also help suppress dendrite formation. Here, a single-ion-conducting polymer electrolyte is blended with lithium-conducting oxide ceramic particles to make a composite electrolyte. This electrolyte is studied in comparison to a composite electrolyte containing freely dissolved lithium salt. It is found that the addition of ceramic particles to the single-ion-conducting polymer can result in increased cation dissociation and consequent increased ionic conductivity. The electrolytes are cycled in lithium symmetrical cells, and it is found that the ceramic-containing electrolytes show increased interfacial stability with the lithium metal compared to the pristine polymer electrolytes. Our findings shed light on how to optimize the polymer host chemistry to form composite electrolytes that can meet the challenging requirements to stabilize the lithium metal anode.

25 ENERGY STORAGE↗

Effect of composition on electrical properties of lead-free Bi{sub 0.5}(Na{sub 0.80}K{sub 0.20}){sub 0.5}TiO{sub 3}-(Ba{sub 0.98}Nd{sub 0.02})TiO{sub 3} piezoelectric ceramics

Lead-free piezoelectric ceramics with the composition of (1-x)Bi{sub 0.5}(Na{sub 0.80}K{sub 0.20}){sub 0.5}TiO{sub 3}-x(Ba{sub 0.98}Nd{sub 0.02})TiO{sub 3} or (1-x) BNKT-xBNdT (with x = 0-0.20 mol fraction) have been synthesized by a conventional mixed-oxide method. The compositional dependence of phase structure and electrical properties of the ceramics were systemically studied. The optimum sintering temperature of all BNKT-BNdT ceramics was found to be 1125 Degree-Sign C. X-ray diffraction pattern suggested that BNdT effectively diffused into BNKT lattice during sintering to form a solid solution with a perovskite structure. Scanning electron micrographs showed a slight reduction of grain size when BNdT was added. It was found that BNKT-0.10BNdT ceramic exhibited optimum electrical properties ({epsilon}{sub r} = 1716, tan{delta} = 0.0701, T{sub c} = 327 Degree-Sign C, and d{sub 33} = 211 pC/N), suggesting that this composition has a potential to be one of a promising lead-free piezoelectric candidate for dielectric and piezoelectric applications.

36 MATERIALS SCIENCE↗

Luminescent, dielectric, and ferroelectric properties of Pr doped Bi{sub 7}Ti{sub 4}NbO{sub 21} multifunctional ceramics

Pr doped Bi{sub 7}Ti{sub 4}NbO{sub 21} (BTN) multifunctional ceramics were prepared by a conventional sintering technique and their luminescent, dielectric, and ferroelectric properties were investigated. The X-ray diffraction data showed that the samples were single phase, and the scanning electron microscopy image indicated that the ceramics had flake-like grains with uniform thickness. The red emission was observed under the ultraviolet and blue light excitation at room temperature. The thermal quench of luminescence was measured and the result indicated that Pr doped BTN ceramics might be potentially applied in luminescent probes and temperature sensors. With the increasing Pr{sup 3+} content, the intensity of the photoluminescence increased initially and then decreased due to concentration quenching; The Curie temperature T{sub c} was slightly shifted to the lower temperature; the ferroelectric properties was almost unchanged by doping. As a new multifunctional material, the Pr doped BTN ceramics could be used for a wide range of application, such as integrated electro-optical devices.

36 MATERIALS SCIENCE↗

Influence of rare earth doping on thermoelectric properties of SrTiO{sub 3} ceramics

Thermoelectric properties of SrTiO{sub 3} ceramics, doped with different rare earth elements, were investigated in this work. It's found that the ionic radius of doping elements plays an important role on thermoelectric properties: SrTiO{sub 3} ceramics doped with large rare earth ions (such as La, Nd, and Sm) exhibit large power factors, and those doped with small ions (such as Gd, Dy, Er, and Y) exhibit low thermal conductivities. Therefore, a simple approach for enhancing the thermoelectric performance of SrTiO{sub 3} ceramics is proposed: mainly doped with large ions to obtain a large power factor and, simultaneously, slightly co-doped with small ions to obtain a low thermal conductivity. Based on this rule, Sr{sub 0.8}La{sub 0.18}Yb{sub 0.02}TiO{sub 3} ceramics were prepared, whose ZT value at 1 023 K reaches 0.31, increasing by a factor of 19% compared with the single-doped counterpart Sr{sub 0.8}La{sub 0.2}TiO{sub 3} (ZT = 0.26)

36 MATERIALS SCIENCE↗

Investigation of photoluminescence of Si−O−C(−H) ceramics at an early stage of decarbonization by using high energy excitation

Si−O−C(−H) ceramics with reduced carbon contents were prepared by pyrolyzing polysiloxane particles in hydrogen at temperatures of 750, 800 and 850 °C. Under HeCd laser irradiation (325 nm), the obtained ceramics show broad spectra peaking at 400–415 nm. On the other hand, the excitation on the higher energy region by an ArF excimer laser (193 nm) induces new PL bands located at short wavelength region of 300 and 355 nm. Such high energy PL bands appear prominently in the ceramics synthesized at 750 °C, and are minor in ceramics synthesized at 800 and 850 °C.

36 MATERIALS SCIENCE↗

Effect of heat treatment time on microstructure and electrical conductivity in LATP glass ceramics

Glass-ceramic is prepared by heat treatment of melt quenched 14Li{sub 2}O−9Al{sub 2}O{sub 3}−38TiO{sub 2}−39P{sub 2}O{sub 5} glass in the vicinity of crystallization temperature. Growth of ceramic phase is controlled by tuning heat treatment time at fixed temperature. Ceramic phase was identified to be LiTi{sub 2}(PO{sub 4}){sub 3} from X Ray Diffraction analysis. Microstructural evolution of this phase with hold time was observed under high resolution Scanning Electron Microscope. DC conductivity is observed to increase by 4-5 orders of magnitude in this glass-ceramic compared to parent glass. However, formation of pores and cracks with very large heat treatment time seem to hinder further increase of conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Separators - Technology review: Ceramic based separators for secondary batteries

Besides a continuous increase of the worldwide use of electricity, the electric energy storage technology market is a growing sector. At the latest since the German energy transition ('Energiewende') was announced, technological solutions for the storage of renewable energy have been intensively studied. Storage technologies in various forms are commercially available. A widespread technology is the electrochemical cell. Here the cost per kWh, e. g. determined by energy density, production process and cycle life, is of main interest. Commonly, an electrochemical cell consists of an anode and a cathode that are separated by an ion permeable or ion conductive membrane - the separator - as one of the main components. Many applications use polymeric separators whose pores are filled with liquid electrolyte, providing high power densities. However, problems arise from different failure mechanisms during cell operation, which can affect the integrity and functionality of these separators. In the case of excessive heating or mechanical damage, the polymeric separators become an incalculable security risk. Furthermore, the growth of metallic dendrites between the electrodes leads to unwanted short circuits. In order to minimize these risks, temperature stable and non-flammable ceramic particles can be added, forming so-called composite separators. Full ceramic separators, in turn, are currently commercially used only for high-temperature operation systems, due to their comparably low ion conductivity at room temperature. However, as security and lifetime demands increase, these materials turn into focus also for future room temperature applications. Hence, growing research effort is being spent on the improvement of the ion conductivity of these ceramic solid electrolyte materials, acting as separator and electrolyte at the same time. Starting with a short overview of available separator technologies and the separator market, this review focuses on ceramic-based separators. Two prominent examples, the lithium-ion and sodium-sulfur battery, are described to show the current stage of development. New routes are presented as promising technologies for safe and long-life electrochemical storage cells.

25 ENERGY STORAGE↗

Mechanical confinement for improved energy storage density in BNT-BT-KNN lead-free ceramic capacitors

With the advent of modern power electronics, embedded circuits and non-conventional energy harvesting, the need for high performance capacitors is bound to become indispensible. The current state-of-art employs ferroelectric ceramics and linear dielectrics for solid state capacitance. However, lead-free ferroelectric ceramics propose to offer significant improvement in the field of electrical energy storage owing to their high discharge efficiency and energy storage density. In this regards, the authors have investigated the effects of compressive stress as a means of improving the energy storage density of lead-free ferroelectric ceramics. The energy storage density of 0.91(Bi{sub 0.5}Na{sub 0.5})TiO{sub 3}-0.07BaTiO{sub 3}-0.02(K{sub 0.5}Na{sub 0.5})NbO{sub 3} ferroelectric bulk ceramic was analyzed as a function of varying levels of compressive stress and operational temperature .It was observed that a peak energy density of 387 mJ.cm{sup -3} was obtained at 100 MPa applied stress (25{sup o}C). While a maximum energy density of 568 mJ.cm{sup -3} was obtained for the same stress at 80{sup o}C. These values are indicative of a significant, 25% and 84%, improvement in the value of stored energy compared to an unloaded material. Additionally, material's discharge efficiency has also been discussed as a function of operational parameters. The observed phenomenon has been explained on the basis of field induced structural transition and competitive domain switching theory.

36 MATERIALS SCIENCE↗

Temperature dependent Raman scattering and far-infrared reflectance spectra of MgO modified Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.98}Nb{sub 0.02}O{sub 3} ceramics: A composition effect

Lattice dynamics and phase transition of MgO modified Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.98}Nb{sub 0.02}O{sub 3} (PZTN-x wt. % MgO, x = 0, 0.1, 0.2, 0.5) ceramics have been investigated by far-infrared (FIR) reflectance in the temperature range of 5.5–300 K and Raman spectra between 77 and 300 K, respectively. With the aid of above complementary methods, the structure of all ceramics was defined as low-temperature ferroelectric rhombohedral phase [F{sub R(LT)}] at room temperature. The FIR dielectric functions were extracted from the multi-Lorentz oscillator dispersion model. The lowest frequency phonon mode, which is related to Pb-BO{sub 3} (B = Zr, Ti, Nb) vibration, mainly dominates the FIR dielectric response. With increasing MgO composition, the dielectric constants ε(0) at room temperature are estimated to 85.4, 73.4, 73.9, and 41.9, respectively. The decreasing trend can be due to the doubly ionized oxygen vacancies induced by Mg substitution for B-site. The order-disorder phase transition located around 120 K can be clearly clarified from temperature evolution of phonon frequency, damping, and intensity. It decreases slightly with increasing MgO composition, which influence the distortion due to the broken correlation chains and local permanent dipoles creation. Moreover, the transformation from antiferroelectric orthorhombic A{sub O} to [ F{sub R(LT)} ] phase has been observed around 250 K, which is associated with the antiferroelectric displacement of Pb atoms along 〈 110 〉 and coupled rotations of the corner-connected oxygen octahedral. Furthermore, the transition from [ F{sub R(LT)} ] to [ F{sub R(HT)} ] (high-temperature ferroelectric rhombohedral phase) was identified around 290 K for MgO-doped PZTN ceramics. It arises from the shift of cation (Pb and Zr/Ti/Nb/Mg ions) along the 〈 111 〉 direction and the transition temperature slightly decreases compared to the pure ceramic.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Porosity and biocompatibility study of ceramic implants based on ZrO{sub 2} and Al{sub 2}O{sub 3}

The work studies ZrO{sub 2}(Me{sub x}O{sub y})-based porous ceramics produced from the powders consisting of hollow spherical particles. It was shown that the structure is represented by a cellular framework with bimodal porosity consisting of sphere-like large pores and pores that were not filled with the powder particles during the compaction. For such ceramics, the increase of pore volume is accompanied by the increased strain in an elastic area. It was also shown that the porous ZrO{sub 2} ceramics had no acute or chronic cytotoxicity. At the same time, ceramics possess the following osteoconductive properties: adhesion support, spreading, proliferation and osteogenic differentiation of MSCs.

36 MATERIALS SCIENCE↗

Porosity and mechanical properties of zirconium ceramics

The article studies the porous ceramics consisting of ultra-fine ZrO{sub 2} powders. The porosity of ceramic samples varied from 15% to 80%. The structure of the ceramic materials had a cellular configuration. The distinctive feature of all experimentally obtained strain diagrams is their nonlinearity at low deformations characterized by the parabolic law. It was shown that the observed nonlinear elasticity for low deformations shown in strain diagrams is due to the mechanical instability of cellular elements of the ceramic framework.

36 MATERIALS SCIENCE↗

Dense and half-dense NiZnCo ferrite ceramics: Their respective relevance for antenna downsizing, according to their dielectric and magnetic properties at microwave frequencies

Spinel ferrite Ni{sub 0.5}Zn{sub 0.3}Co{sub 0.2}Fe{sub 1.98}O{sub 4−x} nanoparticles were synthesized by co-precipitation method, and samples were realized by moulding and annealing at key temperatures (T{sub M} = 800 °C, 900 °C, 1050 °C, determined beforehand through shrinkage measurements) going with calcining and sintering processes. Annealing at 800 °C and 900 °C led to half-dense ceramics (porosity ∼50 vol. %), whereas bulky ferrite was obtained after annealing at 1050 °C. Elemental analysis, X-ray diffraction and ion chromatography analysis were performed. Complex dielectric permittivity (ε*) and magnetic permeability (μ*) were investigated up to 6 GHz. With increasing T{sub M}, a decreasing amount of Fe{sup 2+} was observed, going with increasing sample density. Coupled effects of the Fe{sup 2+} concentration and of the porosity, both on dielectric and magnetic properties, were chiefly investigated and discussed. The materials show almost constant permittivities (ε′ = 5.0, 6.0, and 14.8 for T{sub M} = 800 °C, 900 °C and 1050 °C, respectively). The bulk value at f = 1 GHz (ε′ = 14.8) can be interpreted well according to Shannon's theory. The permittivities of the half-dense ceramics are discussed on the basis of Bruggeman's Effective Medium Theory. The materials annealed at 800 °C and 900 °C show almost constant magnetic permeabilities in the frequency range from 0.2 to 1 GHz (μ′ = 3.4 and 6.0 for T{sub M} = 800 °C and 900 °C). The observed permeability behavior is typical of monodomain particles, except for the sample annealed at 1050 °C, for which domain wall contribution to μ* is suspected because of non-negligible losses at low frequency (μ″ = 1.3–1.8 at f < 0.3 GHz). This finding is supported by estimations of the upper and lower values for the critical grain size, on the basis of Brown–Van der Zaag's theory. Facing bulk ceramics, and in view of using Ni{sub 0.5}Zn{sub 0.3}Co{sub 0.2}Fe{sub 1.98}O{sub 4−x} ferrite as substrate for antenna miniaturization, the electromagnetic properties of half-dense ceramics materials seem to be very competitive at frequencies beyond 0.2 GHz, and up to 0.7–0.8 GHz.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Rietveld refinement and dielectric properties of (Na{sub 0.5}Bi{sub 0.5}TiO{sub 3})-(Bi{sub 0.8}Ba{sub 0.2}FeO{sub 3}) ceramics

(1-x)(Na{sub 0.5}Bi{sub 0.5}TiO{sub 3})-x(Bi{sub 0.8}Ba{sub 0.2}FeO{sub 3}) lead free ceramics (NBT, NBT-BBFO; x = 0.0, 0.1 respectively) have been synthesized by conventional solid state reaction method. Crystalline phase of sintered ceramics was investigated at room temperature using X-ray diffraction. Rietveld refinement of XRD data performed by FullProf revealed that both the samples exhibited rhombohedral structure with R3c space group. Dielectric properties of these ceramics were studied at different temperatures in a wide frequency range using impedance analyzer. Dielectric constant and dielectric loss were found to be increase with increase of BBFO content. The prepared ceramics exhibit a broad maximum in dielectric permittivity at 593K and dispersive permittivity at high temperatures. The NBT-BBFO sample shows a relaxor ferroelectric behavior at different frequencies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Bright reddish-orange emission and good piezoelectric properties of Sm{sub 2}O{sub 3}-modified (K{sub 0.5}Na{sub 0.5})NbO{sub 3}-based lead-free piezoelectric ceramics

Reddish orange-emitting 0.948(K{sub 0.5}Na{sub 0.5})NbO{sub 3}-0.052LiSbO{sub 3}-xmol%Sm{sub 2}O{sub 3} (KNN-5.2LS-xSm{sub 2}O{sub 3}) lead-free piezoelectric ceramics with good piezoelectric properties were fabricated in this study, and the photoluminescence and electrical properties of the ceramics were systematically studied. Results showed that Sm{sub 2}O{sub 3} substitution into KNN-5.2LS induces a phase transition from the coexistence of orthorhombic and tetragonal phases to a pseudocubic phase and shifts the polymorphic phase transition (PPT) to below room temperature. The temperature stability and fatigue resistance of the modified ceramics were significantly improved by Sm{sub 2}O{sub 3} substitution. The KNN-5.2LS ceramic with 0.4 mol. % Sm{sub 2}O{sub 3} exhibited temperature-independent properties (25–150 °C), fatigue-free behavior (up to 10{sup 6} cycles), and good piezoelectric properties (d{sub 33}{sup * }= 230 pm/V, d{sub 33} = 176 pC/N, k{sub p} = 35%). Studies on the photoluminescence properties of the samples showed strong reddish-orange emission upon blue light excitation; these emission intensities were strongly dependent on the doping concentration and sintering temperature. The 0.4 mol. % Sm{sub 2}O{sub 3}-modified sample exhibited temperature responses over a wide temperature range of 10–443 K. The maximum sensing sensitivity of the sample was 7.5 × 10{sup −4} K at 293 K, at which point PPT occurred. A relatively long decay lifetime τ of 1.27–1.40 ms and a large quantum yield η of 0.17–0.19 were obtained from the Sm-modified samples. These results suggest that the KNN-5.2LS-xSm{sub 2}O{sub 3} system presents multifunctional properties and significant technological potential in novel multifunctional devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The down-conversion and up-conversion photoluminescence properties of Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}:Yb{sup 3+}/Pr{sup 3+} ceramics

Na{sub 0.5}Bi{sub 0.5−x−y}Yb{sub x}Pr{sub y}TiO{sub 3} (NBT:xYb/yPr) ceramics with different Yb and Pr contents are prepared. Both the down-conversion (DC) and up-conversion (UC) photoluminescence (PL) of the ceramics via 453 and 980 nm excitation, respectively, are investigated. The effect of Yb{sup 3+} and Pr{sup 3+} doping contents on the DC and UC PL is significantly different from each other. Furthermore, the UC PL of the ceramics as a function of temperatures is measured to investigate the UC process in detail. Based on energy level diagram of Pr{sup 3+} and Yb{sup 3+} ions and the DC and UC PL spectra, the DC and UC PL mechanisms of Pr{sup 3+} and Yb{sup 3+} ions are discussed. Especially, the UC PL mechanism is clarified, which is different from the previously reported literature. Also, the temperature sensing properties of the ceramics are studied based on the photoluminescence ratio technique, using the thermal coupling energy levels of Pr{sup 3+}.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Rare-earth doped transparent ceramics for spectral filtering and quantum information processing

Homogeneous linewidths below 10 kHz are reported for the first time in high-quality Eu{sup 3+} doped Y {sub 2}O{sub 3} transparent ceramics. This result is obtained on the {sup 7}F{sub 0}→{sup 5}D{sub 0} transition in Eu{sup 3+} doped Y {sub 2}O{sub 3} ceramics and corresponds to an improvement of nearly one order of magnitude compared to previously reported values in transparent ceramics. Furthermore, we observed spectral hole lifetimes of ∼15 min that are long enough to enable efficient optical pumping of the nuclear hyperfine levels. Additionally, different Eu{sup 3+} concentrations (up to 1.0%) were studied, resulting in an increase of up to a factor of three in the peak absorption coefficient. These results suggest that transparent ceramics can be useful in applications where narrow and deep spectral holes can be burned into highly absorbing lines, such as quantum information processing and spectral filtering.

36 MATERIALS SCIENCE↗

The influence of temperature induced phase transition on the energy storage density of anti-ferroelectric ceramics

Anti-ferroelectric (AFE) composite ceramics of (Pb{sub 0.858}Ba{sub 0.1}La{sub 0.02}Y{sub 0.008})(Zr{sub 0.65}Sn{sub 0.3}Ti{sub 0.05})O{sub 3}-(Pb{sub 0.97}La{sub 0.02})(Zr{sub 0.9}Sn{sub 0.05} Ti{sub 0.05})O{sub 3} (PBLYZST-PLZST) were fabricated by the conventional solid-state sintering process (CS), the glass-aided sintering (GAS), and the spark plasma sintering (SPS), respectively. The influence of the temperature induced phase transition on the phase structure, hysteresis loops, and energy storage properties of the composite ceramics were investigated in detail. The measured results of X-ray diffraction demonstrate that the composite ceramics exhibit the perovskite phases and small amounts of non-functional pyrochlore phases. Compared with the CS process, the GAS and SPS processes are proven more helpful to suppress the diffusion behaviors between the PBLYZST and PLZST phases according to the field emission scanning electron microscopy, thereby being able to improve the contribution of PBLYZST phase to the temperature stability of the orthogonal AFE phase. When the ambient temperature rises from 25 °C to 125 °C, CS and GAS samples have undergone a phase transition from orthorhombic AFE phase to tetragonal AFE phase, which results in a sharp decline in the energy storage density. However, the phase transition temperature of SPS samples is higher than 125 °C, and the energy storage density only slightly decreases due to the disorder of material microstructure caused by the high temperature. As a result, the SPS composite ceramics obtain a recoverable high energy storage density of 6.46 J/cm{sup 3} and the excellent temperature stability of the energy storage density of 1.16 × 10{sup −2} J/°C·cm{sup 3}, which is 1.29 × 10{sup −2} J/°C·cm{sup 3} lower than that of CS samples and about 0.43 times as that of GAS samples.

36 MATERIALS SCIENCE↗

The structure and properties of boron carbide ceramics modified by high-current pulsed electron-beam

The present work is devoted to numerical simulation of temperature fields and the analysis of structural and strength properties of the samples surface layer of boron carbide ceramics treated by the high-current pulsed electron-beam of the submillisecond duration. The samples made of sintered boron carbide ceramics are used in these investigations. The problem of calculating the temperature field is reduced to solving the thermal conductivity equation. The electron beam density ranges between 8…30 J/cm{sup 2}, while the pulse durations are 100…200 μs in numerical modelling. The results of modelling the temperature field allowed ascertaining the threshold parameters of the electron beam, such as energy density and pulse duration. The electron beam irradiation is accompanied by the structural modification of the surface layer of boron carbide ceramics either in the single-phase (liquid or solid) or two-phase (solid-liquid) states. The sample surface of boron carbide ceramics is treated under the two-phase state (solid-liquid) conditions of the structural modification. The surface layer is modified by the high-current pulsed electron-beam produced by SOLO installation at the Institute of High Current Electronics of the Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia. The elemental composition and the defect structure of the modified surface layer are analyzed by the optical instrument, scanning electron and transmission electron microscopes. Mechanical properties of the modified layer are determined measuring its hardness and crack resistance. Research results show that the melting and subsequent rapid solidification of the surface layer lead to such phenomena as fragmentation due to a crack network, grain size reduction, formation of the sub-grained structure due to mechanical twinning, and increase of hardness and crack resistance.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗