Studies on polycrystalline layered ceramic oxide: LiFeVO4

Abstract

A new polycrystalline layered ceramic oxide, LiFeVO₄, has been prepared by a standard solid state reaction technique. The preparation conditions were optimised using thermogravimmetric analysis (TGA) technique. Material formation under the reported conditions was confirmed by X-ray diffraction studies. A preliminary structural analysis indicated that the crystal structure was orthorhombic with lattice parameters: a=4·3368 Å, b=13·1119 Å and c=16·3426 Å. The phase morphology and surface property were studied by scanning electron microscopy. Complex impedance analysis of the sample indicated bulk contribution to electrical properties at T≤125°C, grain boundary effects at the temperatures ≥125°C, negative temperature coefficient of resistance (NTCR) effect and evidence of temperature dependent electrical relaxation phenomena in the sample. The dc conductivity σ_dc shows typical Arrhenius behaviour when observed as a function of temperature. The activation energy value was estimated to be 0·24 eV. The value of σ_dc, evaluated from complex impedance spectrum, shows a jump of nearly two orders of magnitude at higher temperature (～1·24 × 10^?5 S cm^?1 at 350°C) when compared with that of σ_dc (1·14 × 10^?6 S cm^?1 at 50°C). Alternating current conductivity spectrum obeys Jonscher's universal power law. The results of σ_ac v. temperature are also discussed.     

Investigation of layered perovskite NdBa0.5Sr0.25Ca0.25Co2O5+δ as cathode for solid oxide fuel cells

Layered perovskite oxides with and without Ca-doped NdBa_0.5Sr_0.25Ca_0.25Co₂O_5+δ (NBSCaCO) and NdBa_0.5Sr_0.5Co₂O_5+δ (NBSCO) are studied to investigate the effects of Ca doping on the crystal structure, thermal behavior, electrical and electrochemical properties. Both NBSCO and NBSCaCO are tetragonal structure with P4/mmm space group. The average thermal expansion coefficient (TEC) value is reduced from 23.3?×?10^?6 K^?1 to 19.8?×?10^?6 K^?1 during 30–800?°C. The electrical conductivities are increased by Ca doping. Both electrical conductivities of NBSCO and NBSCaCO are higher than 600?S·cm^?1 over 30–800?°C. Substitution of Sr with Ca can effectively improve the electrochemical properties of NBSCaCO. From 650?°C to 800?°C, the area specific resistance (ASR) of NBSCaCO are decreased from 0.62 to 0.062?Ω?cm² and the corresponding output power density are increased from 258 to 812?mW?cm^?2. On the basis of these results, Ca doped layered perovskite NBSCaCO can be a good cathode candidate material for SOFC application.     

Phthalonitrile end-capped sulfonated polyarylene ether nitriles for low-swelling proton exchange membranes

A series of phthalonitrile end-capped sulfonated polyarylene ether nitriles are synthesized via K₂CO₃ mediated nucleophilic aromatic substitution reaction at various molar ratios. The as-prepared polymer structures are confirmed by ¹H NMR and FTIR spectroscopy. The properties of membranes cast from the corresponding polymers are investigated with respect to their structures. The membranes exhibit good thermal and mechanical properties, low methanol permeability (0.01?×?10^?6–0.58?×?10^?6 cm²·s^?1 at 20 °C), and high proton conductivity (0.021–0.088 S·cm^?1 at 20 °C). The introduction of phthalonitrile is proved to increase intermolecular interaction, mainly contributing to the reduction in water uptake, swelling ratio, and methanol permeability. More importantly, its introduction does not decrease the proton conductivity, but there is a slight increase. Furthermore, the selectivity of SPEN-CN-50 can reach 4.11?×?10⁵ S·s·cm^?3, which is about nine times higher than that of Nafion 117. All the data show that the as-prepared membranes may be potential proton exchange membrane for DMFCs applications.     

Electrochemical characterization of BaCe0·7Zr0·1Y0·16Zn0·04O3-δ electrolyte synthesized by combustion spray pyrolysis

BaCe_0·7Zr_0·1Y_0·16Zn_0·04O_3-δ perovskite has been investigated due to its potential as an electrolyte in industrial steam electrolysis applications. The lowest area specific resistance (ASR) is achieved as 4.0 Ω cm² at 711 °C under 3% wet Ar atmosphere. The conductivity is calculated as 2.93 × 10^?2 S cm^?1 and kept stable for a ~70 h testing period. ASR increased at lower temperature (511 °C) under the same atmosphere and a new impedance arc (with 4.5 Ω cm² ASR and 2 × 10^?8 F equivalent capacitance) is formed, indicating second phase formation. No second phase formation is observed at the same temperature under dry 5% H₂ in Ar. The second phase formation/degradation of the electrolyte is attributed to Ba(OH)₂ and CeO₂ formations around 500 °C under wet atmospheres. At elevated temperatures, ~700 °C, BaCe_0·7Zr_0·1Y_0·16Zn_0·04O_3-δ exhibits both excellent protonic conductivity and stability which makes it a great candidate for both industrial fuel cells and steam electrolysers.     

Thermal and electrical properties of additive-free rapidly hot-pressed SiC ceramics

The thermal and electrical properties of newly developed additive free SiC ceramics processed at a temperature as low as 1850 °C (RHP0) and SiC ceramics with 0.79 vol.% Y₂O₃-Sc₂O₃ additives (RHP79) were investigated and compared with those of the chemically vapor-deposited SiC (CVD-SiC) reference material. The additive free RHP0 showed a very high thermal conductivity, as high as 164 Wm⁻¹ K⁻¹, and a low electrical resistivity of 1.2 × 10⁻¹ Ω cm at room temperature (RT), which are the highest thermal conductivity and the lowest electrical resistivity yet seen in sintered SiC ceramics processed at ≤1900 °C. The thermal conductivity and electrical resistivity values of RHP79 were 117 Wm⁻¹ K⁻¹ and 9.5 × 10⁻² Ω cm, respectively. The thermal and electrical conductivities of CVD-SiC parallel to the direction of growth were ∼324 Wm⁻¹ K⁻¹ and ∼5 × 10⁻⁴Ω⁻¹ cm⁻¹ at RT, respectively.     

Effects of Y2O3–RE2O3 (RE = Sm,Gd, Lu) Additives on Electrical and Thermal Properties of Silicon Carbide Ceramics

In this study, we investigated the electrical and thermal properties of SiC ceramics with 2 vol% equimolar Y₂O₃–RE₂O₃ (RE = Sm, Gd, Lu) additives. The three SiC ceramics with 2 vol% equimolar Y₂O₃–RE₂O₃ additives showed electrical conductivities on the order of ~10³ (Ω·m)^?1, which is one order of magnitude higher than that of the SiC ceramics sintered with 2 vol% Y₂O₃ only. The increase in electrical conductivity is attributed to the growth of heavily nitrogen‐doped SiC grains during sintering and the confinement of oxide additives in the junction area. The thermal conductivities of the SiC ceramics were in the 176–198 W·(m·K)^?1 range at room temperature. The new additive systems, equimolar Y₂O₃–RE₂O₃, are beneficial for achieving both high electrical conductivity and high thermal conductivity in SiC ceramics.     

Thermal Insulation Characteristics of Polybenzoxazine Aerogels

Polybenzoxazine (PBO) aerogels with low densities and low thermal conductivities are prepared from Bisphenol A (BPA) benzoxazine monomers by ring‐opened polymerisation using HCl as a catalyser at 10 °C. The obtained PBO aerogels have cross‐linked and 3D network structures with the densities ranging from 0.084 to 0.526 g cm^?3. The thermal conductivities under different pressures (3–10⁵ Pa, air) and different atmospheres (N₂, Ar, and CO₂, 10⁵ Pa) are investigated. The thermal conductivities are in the range of 0.0335–0.0652 W m K^?1 under ambient pressure and 0.0098–0.0571 W m K^?1 at 3 Pa. The thermal transfer mechanism under different gas pressures is analyzed with increasing pressure. Under different atmospheres, the thermal conductivities decrease as the molecular weight of the gas increases. Compared with the traditional organic foam insulating materials of phenolic foam, polyurethane and polystyrene, which have similar apparent densities, PBO aerogels exhibit lower thermal conductivity of 0.0335 W m K^?1 than that of traditional organic foam at room temperature.     

Improved electrical and thermal conductivities of polysiloxane-derived silicon oxycarbide ceramics by barium addition

The electrical and thermal conductivities of bulk barium-added silicon oxycarbide (SiOC-Ba) ceramics are investigated. The SiOC-Ba ceramics exhibited improved electrical and thermal conductivities upon increasing the sintering temperature from 1450 °C to 1650 °C. Precipitation of graphitic carbon clusters observed by Raman spectroscopy and high-resolution transmission electron microscopy is attributed to the phase separation during the fabrication process. The increase in the electrical conductivity can be rationalized in terms of an increase in the density of the sp² CC bonds within the carbon clusters. The increase in the thermal conductivity is mainly attributed to the formation of interconnected graphitic clusters in the SiOC matrix and SiC embedded in the clusters. The electrical and thermal conductivities of the SiOC-Ba ceramics sintered at 1650 °C are 14.0 Ω^?1 cm^?1 and 5.6 W/m K, respectively, at room temperature. The electrical conductivity of SiOC-Ba sintered at 1550 °C is 5.3 Ω^?1 cm^?1 and 7.0 Ω^?1 cm^?1 at 2 and 300 K, respectively.     

Electrical and thermophysical properties of mechanochemically obtained lanthanide hafnates

This contribution presents the synthesis and thermophysical characterization of seven lanthanide hafnates Ln₂Hf₂O₇ (Ln=Sm³⁺, Eu³⁺, Gd³⁺, Dy³⁺, Y³⁺, Ho³⁺, Yb³⁺); the title samples were prepared at room temperature by mechanically milling stoichiometric mixtures of the corresponding elemental oxides. Irrespective of the lanthanide ion involved, milling promotes the formation of highly disordered fluoritelike materials. Postmilling thermal treatments facilitate the formation of the fluorite ordered derivative, the pyrochlore structure, but only for the larger lanthanides (Sm³⁺, Eu³⁺, Gd³⁺). Impedance spectroscopy measurements revealed that these materials show a moderate‐to‐good oxygen ion conductivity at high temperatures; furthermore, those adopting the pyrochlore structure give higher σ_dc and lower E_dc than their fluorite analogues (σ_dc at 750°C>10^?3 S·cm^?1 vs <5·10^?4 S·cm^?1, respectively). The same trend also holds for the thermal resistivity at high temperatures; the highest thermal resistivity and thus, lowest κ was obtained for Eu₂Hf₂O₇ (κ~1.3·W·m^?1·K^?1 at 800°C). Therefore, Ln₂Hf₂O₇ phases might be attractive component materials for electrochemical devices and thermal insulating coatings.     

Electrical characterization of multidoped ceria ceramics

Ceria ceramics was obtained from multi-doped nanosized ceria powders prepared by both modified glycine nitrate procedure (MGNP) and self-propagating reaction at room temperature (SPRT). Rare earth elements such as Nd, Sm, Gd, Dy, Y, Yb were used as dopants. The overall mole fraction of dopants was 0.2. One-hour long sintering of powder compacts was performed at 1500 °C in oxygen atmosphere. Phase composition, microstructure and ionic conductivity of sintered samples were analysed. Single-phase ceria was detected in all samples. In general, the increase in the number of dopants improved the ionic conductivity. The samples doped simultaneously with five dopants had the highest ionic conductivity, as evidenced by the impedance measurements. At 450 °C, the conductivity of sample obtained by MGNP was 3.94×10^?3 Ω^?1 cm^?1 whereas the conductivity of sample obtained by SPRT was 2.61×10^?3 Ω^?1 cm^?1. The conductivity activation energy for MGNP and SPRT samples was measured to be 0.348 and 0.385 eV, respectively. Finally, the conductivity decreased as the number of dopants increased to six.     

Crystal structure,microstructure, thermal expansion and electrical conductivity of CeO2–ZrO2 solid solution

CeO₂–ZrO₂ solid solution was synthesised by mechanical activation solid-state chemical reaction method and characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal dilatometer, Hebb–Wagner method and DC van der Pauw method. The effects of CeO₂ content on the crystal structure, microstructure, thermal expansion coefficient (TEC), electronic conductivity and total conductivity were investigated. XRD analysis showed that (25 and 75?mol-%) CeO₂–ZrO₂ solid solutions corresponded to tetragonal and cubic phase, and 50?mol-% CeO₂–ZrO₂ belonged to the mixture of tetragonal and cubic phases. SEM analysis showed that doping CeO₂ was helpful to the sinterability of CeO₂–ZrO₂ samples. The TECs increased from 13.27?×?10^?6 to 14.72?×?10^?6?K^?1 with increasing CeO₂ content. The electronic and total conductivities of 75?mol-% CeO₂–ZrO₂ were largest, reaching 1.02?×?10^?4?S?cm^?1 and 1.02?×?10^?2?S?cm^?1 at 850°C, respectively.     

Electrically conductive SiC ceramics processed by pressureless sintering

Polycrystalline SiC ceramics with 10 vol% Y₂O₃-AlN additives were sintered without any applied pressure at temperatures of 1900-2050°C in nitrogen. The electrical resistivity of the resulting SiC ceramics decreased from 6.5 × 10¹ to 1.9 × 10⁻² Ω·cm as the sintering temperature increased from 1900 to 2050°C. The average grain size increased from 0.68 to 2.34 μm with increase in sintering temperature. A decrease in the electrical resistivity with increasing sintering temperature was attributed to the grain-growth-induced N-doping in the SiC grains, which is supported by the enhanced carrier density. The electrical conductivity of the SiC ceramic sintered at 2050°C was ~53 Ω⁻¹·cm⁻¹ at room temperature. This ceramic achieved the highest electrical conductivity among pressureless liquid-phase sintered SiC ceramics.     

Study of hyperbranched poly(glycidol) sulfate electrolyte

Hyperbranched poly(glycidol) alkali sulfate (SHPG‐M) was prepared based on hyperbranched poly(glycidol). Polyurethane–hyperbranched poly(glycidol) (PU–SHPG‐M) sulfate electrolyte is a kind of single ionic or cationic conducting polymer electrolyte. Such a single ionic polymer electrolyte can obviously reduce the polarization and has little decay of direct current (DC) conductivity. SHPG‐M was characterized by Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), atomic force microscopy (AFM) and impedance analysis. The optimum conductivity is ～3 × 10^?6 S·cm^?1, with 30–40% SHPG‐M in the polymer electrolyte at room temperature. The species of cation greatly effects the ionic conductivity of the polymer electrolyte; that is, σ_SHPG‐Li > σ_SHPG‐Na > σ_SHPG‐K, with same SHPG‐M content in the polymer electrolyte. The ionic conductivity increases with an increase of temperature, and the dependence of ionic conductivity on temperature fits the Arrhenius equation well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1185–1190, 2003     

Ionic conductivity of oxides based on Li4SiO4

Lithium orthosilicate, Li₄SiO₄, and its solid solutions are a new group of solids of high ionic conductivity. Either Li or Si may be at least partially replaced by several other di-, tri- or tetra-valent cations. Highest conductivities were found for solid solutions with Si partially replaced by Ti; typical values were 10^?3 to 10^?4 Ω^?1 cm^?1 at 300°C rising toc. l Ω^?1 cm^?1 by 700°C. The solid solutions are easy to prepare and are stable in air. Conductivities were measured on pressed cubes of powdered material using variable frequency a.c. methods. The conductivities of these Li₄SiO₄ solid solutions are compared with those of other known Li-conducting solids; Li₄SiO₄ solid solutions are probably the best all-round, polycrystalline Li-electrolytes yet found for temperatures abovec. 200°C.     

Fabrication and characterization of a solid polymeric electrolyte of PAN‐TiO2‐LiClO4

The ionic conductivity of PAN‐TiO₂‐LiClO₄ as a function of TiO₂ concentration and temperature has been reported. The electrolyte samples were prepared by solution casting technique. Their conductivity was measured using the impedance spectroscopy technique. The highest room temperature conductivity of 1.8 × 10^?4 S cm^?1 was obtained at 7.5 wt % of TiO₂ filler. It was observed that the relationship between temperature and conductivity were linear, fitting well in Arrhenius and not in Vogel‐Tamman‐Fulcher equation. The pre‐exponential factor, σ₀ and E_a are 1.8 × 10^?4 S cm^?1 and 0.15 eV, respectively. The conductivity data have been supported by differential scanning calorimeter (DSC) analysis. DSC analysis showed that there was a significant change in glass transition temperature (T_g) with the filler concentration. The SEM micrograph revealed that the TiO₂ particles are dispersed in the electrolyte, thus enhancing its conductivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Sulfonated copoly(norbornene)s bearing sultone pendant groups and application as proton exchange membranes candidates

Novel copolynorbornenes bearing pendant sultone groups (designated as P(BN/SulNBOH) and P(BN/SulNBOMe)) have been successfully synthesized via copolymerization of functionalized norbornenes bearing sultones (designated as SulNBOH and SulNBOMe) with 2-butoxymethylene norbornene (BN). The catalyst system showed high catalyst activity (10⁴ g_polymer/mol_Ni·h) and the obtained copolymers have high molecular weight and a narrow molecular weight distribution. Furthermore, the achieved copolymers P(BN/SulNBOH) and P(BN/SulNBOMe) were converted into sulfonated copolymers sP(BN/NBOH) and sP(BN/NBOMe). Both sP(BN/NBOH) and sP(BN/NBOMe) membranes displayed low water uptake, high thermal properties, good mechanical properties, and better proton exchange membranes properties. The proton conductivities measured in the hydrated state at 80?°C ranged from 10^?5 to 7.19?×?10^?3?S·cm^?1.

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.     

Compatibility and conductivity of La2Ni1−xFexO4+δ and LaNi0·6Fe0·4O3−δ with GDC electrolyte

The compatibilities and conductivities of K₂NiF₄ typed La₂Ni_0·9Fe_0·1O_4+δ (L₂NF91) and LaNi_0·6Fe_0·4O_3?δ (LNF64) perovskites, promising cathode materials for solid oxide fuel cell, with Gd_0·1Ce_0·9O_1·95 (GDC) electrolyte were investigated. L₂NF91 and LNF64 were synthesised using citrate and modified citrate methods with the calcination temperature of 1000°C for 5 h. The single phased oxides with the average particle sizes of L₂NF91 and LNF64 ～0·2 μm were obtained. The thermal expansion coefficients of L₂NF91 and LNF64 were 12·7×10^?6 and 13·2×10^?6 K^?1 respectively. The mixtures of cathode materials and the electrolytes were heated between 800 and 1200°C to observe the formation of secondary phases at the operation temperatures of solid oxide fuel cell. The X-ray diffraction and scanning electron microscopy–energy dispersive X-ray results indicated that L₂NF91 and LNF64 had good chemical compatibility with GDC from room temperature up to 900°C. Both L₂NF91 and LNF64 showed higher conductivities when in contact with GDC electrolyte than with Zr_0·92Y_0·08O_1·96 electrolyte.     

Synergistically optimizing electrical and thermal transport properties of Bi2O2Se ceramics by Te‐substitution

Bi₂O₂Se oxyselenides, characterized with intrinsically low lattice thermal conductivity and large Seebeck coefficient, are potential n‐type thermoelectric material in the mediate temperature range. Given the low carrier concentration of ~10¹⁵ cm^?3 at 300 K, the intrinsically low electrical conductivity actually hinders further enhancement of their thermoelectric performance. In this work, the isovalent Te‐substitution of Se plays an effective role in narrowing the band gap, which notably increases the carrier concentration to ~10¹⁸ cm^?3 at 300 K and the electron conduction activation energy has been lowered significantly from 0.33 to 0.14 eV. As a consequence, the power factor has been improved from 104 μW·K^?2·m^?1 for pristine Bi₂O₂Se to 297 μW·K^?2·m^?1 for Bi₂O₂Se_0.96Te_0.04 at 823 K. Meanwhile, the suppressed lattice thermal conductivity derives from the introduced point defects by heavier Te atoms. The gradually decreased phonon mean free path reflects the increasingly intense phonon scattering. Ultimately, the ZT value attains 0.28 for Bi₂O₂Se_0.96Te_0.04 at 823 K, an enhancement by a factor of ~2 as compared to that of pristine Bi₂O₂Se. This study has demonstrated that Te‐substitution of Se could synergistically optimize the electrical and thermal properties thus effectively enhancing the thermoelectric performance of Bi₂O₂Se.     

Composite polymer electrolytes based on the low crosslinked copolymer of linear and hyperbranched polyurethanes

Low crosslinked copolymer of linear and hyperbranched polyurethane (CHPU) was prepared, and the ionic conductivities and thermal properties of the composite polymer electrolytes composed of CHPU and LiClO₄ were investigated. The FTIR and Raman spectra analysis indicated that the polyurethane copolymer could dissolve more lithium salt than the corresponding polymer electrolytes of the non crosslinked hyperbranched polyurethane, and showed higher conductivities. At salt concentration EO/Li = 4, the electrolyte CHPU30‐LiClO₄ reached its maximum conductivity, 1.51 × 10^?5 S cm^?1 at 25°C. DSC measurement was also used for the analysis of the thermal properties of polymer electrolytes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3607–3613, 2007