Influence of Gd3+ and Dy3+ co-doping and sintering regime on enhancement of electrical conductivity of ceria-based solid electrolyte

In order to improve the conductivity of ceria-based solid electrolytes, effect of co-doped Gd³⁺ and Dy³⁺ was evaluated. For this purpose, nano-crystalline Gd_0.2???x Dy _x Ce_0.8O_1.9 powders with various composition ranges (x?=?0.05, 0.1, 0.15, 0.2) were initially synthesized by high-energy milling method. The effect of micro-structural evolution and co-doping on electrical properties of the dense sintered samples fabricated by two-step sintering and conventional sintering of the synthesized powders were investigated. Electrical conductivity of the samples was discussed based on the results obtained by AC impedance spectroscopy at temperatures in the range of 300–700 °C. The co-doping and sintering regime were found to significantly influence the conductivity of the electrolytes. The electrical conductivity of the co-doped samples depends on Dy³⁺ content and the maximum conductivity obtained by 0.15 mol% Dy and 0.05 mol% Gd. The conductivity of Gd_0.2???x Dy _x Ce_0.8O_1.9 (x?=?0.15) was 0.03 S/cm at 700 °C. A thorough discussion was made, based on the present experimental data.     

The chemical stability and conductivity improvement of protonic conductor BaCe0.8 − x Zr x Y0.2O3 − δ

A series of BaCe_0.8???x Zr _x Y_0.2O_3???δ (BCZYx) (x?=?0, 0.2, 0.4, 0.6, 0.8) powders were prepared by EDTA–citrate complexing sol–gel process in this paper. The electrical conducting behavior, as well as chemical stability, was investigated. X-ray diffraction (XRD) results reveal that all samples are homogenous perovskite phases. Observed from XRD patterns and thermogravimetric curves, the samples with x?≥?0.4 survive in the pure CO₂, while samples with various Zr contents all present structurally stable against steam at 800 °C. The Zr-free sample of BaCe_0.8Y_0.2O_3???δ possesses the maximum bulk conductivity, 4.25?×?10^?2 S/cm, but decomposes into Ba(OH)₂ and Ce_0.8Y_0.2O_3???δ in steam. A negative influence of increasing Zr content on the conductivity of BCZYx can be observed by impedance tests. Considering the effect of temperature on the bulk conductivity, BCZY0.4 is preferred to be applied in SOFC as a protonic conductor, ranging from 1.52?×?10^?4 to 1.51?×?10^?3 S/cm (500–850 °C) with E _a?=?0.859 eV, which is proved to be a good protonic conductor with t _H+?≥?0.9.     

An oxygen permeable membrane La0.8Sr0.2(Ga0.8Mg0.2)1 − xCrxO3 − δ for a reduced atmosphere

Mixed electron hole and oxide ion conducting perovskite-type oxides, La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ (0 ≤ x ≤ 1.0)_, were prepared by solid state reaction. The phase stability and the oxygen permeation properties of the oxides were examined as a function of the content of Cr. La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ has a perovskite related tetragonal phase with x = 0.1 to 0.8. The total electrical conductivity of La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ increases with increasing x. The oxygen permeation flux across the La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ membranes at higher temperatures increases with x up to x = 04. The maximum oxygen permeation flux of 1.6 × 10^? 7 mol^? 1 cm^? 2 at 1100 °C in a oxygen activity gradient of air/10^? 2 Pa is observed in La_0.8Sr_0.2(Ga_0.8Mg_0.2)_0.6Cr_0.4O_3 ? δ. This perovskite-type oxide is stable under an oxygen partial pressure of 7 × 10^? 10 Pa at 1000 °C.     

Low temperature microwave sintering of yttrium and samarium co-doped ceria solid electrolytes for IT-SOFCs

Nanocrystalline co-doped ceria Ce_0.8Sm_0.2?xY_xO_2?δ solid electrolytes for intermediate-temperature solid oxide fuel cells (IT-SOFCs) were synthesized through sol–gel auto-combustion method. The prepared samples were sintered via microwave sintering at 1200 °C for 1 h. The X-ray diffraction analysis of co-doped ceria system reveals formation of the samples with a single-phase cubic fluorite structure. The lattice parameter values were calculated from X-ray diffraction patterns. The calculated crystallite sizes of all the samples were found to be in the range of 17 and 28 nm. Surface morphologies and elemental analysis of all the samples were carried out by using SEM and EDS analysis. The existence of chemical bonding in the samples was studied by FTIR spectroscopy. The presence of oxygen vacancies and evaluation of their concentration in the material was carried out using Raman spectroscopy analysis. Electrical properties of all the samples were analyzed by impedance spectroscopy. It was found that microwave sintered co-doped ceria sample Ce_0.8Sm_0.1Y_0.1O_2?δ exhibits the highest total ionic conductivity with minimum activation energy among all the compositions and conventional sintered sample. Therefore, it can be concluded that the microwave sintered Ce_0.8Sm_0.1Y_0.1O_2?δ sample may be useful as a promising electrolyte material for the IT-SOFCs.     

Effect of La3+ and Pr3+ co-doping on structural,thermal and electrical properties of ceria ceramics as solid electrolytes for IT-SOFC applications

In the present investigation, the effect of La³⁺ and Pr³⁺ co-doping on structural, thermal and electrical properties of ceria ceramics useful as solid electrolytes in intermediate temperature solid oxide fuel cells (IT-SOFCs) has been studied. The co-doped ceria Ce_0.8Pr_0.2–xLa_xO_2-δ samples have been prepared successfully via sol-gel auto-combustion synthesis. The high dense ceramic samples have been achieved by carry out an optimized conventional sintering at 1300 °C for 4 h. The powder X-ray diffraction analysis of all the co-doped ceria ceramics revealed the single phase with cubic-fluorite structure formation. Crystallographic information has been carried out from the powder X-ray diffraction and Rietveld refinement analysis. The scanning electron microscope and energy dispersive spectroscopy analysis revealed the smaller grain size with high density in microstructure and stoichiometric elemental confirmations. Raman spectra of prepared ceramics revealed the information of phase and oxygen vacancy formation in the entire compositions. The dilatometric studies of prepared co-doped ceria ceramics revealed the moderate coefficients of thermal expansion. The electrical parameters such as total conductivities and activation energies have been studied with the help of impedance spectroscopy. Among all these co-doped ceria ceramic samples, Ce_0.80Pr_0.10La_0.10O_2−δ found to exhibit the highest value of total ionic conductivity with minimum activation energy and this makes it could be a promising electrolyte material for IT-SOFC applications.     

Novel layered perovskite GdBaCuFeO5+x as a potential cathode for proton-conducting solid oxide fuel cells

A layered perovskite GdBaCuFeO_5+x (GBCuF) was developed as a cathode material for intermediate-temperature solid oxide fuel cells based on a proton-conducting electrolyte of stable BaZr_0.1Ce_0.7Y_0.2O_3?δ (BZCY). The X-ray diffraction results showed that GBCuF was chemically compatible with BZCY after co-fired at 1,000 °C for 10 h. The thermal expansion coefficient of GBCuF, which showed a reasonably reduced value (15.1?×?10^?6 K^?1), was much closer to that of BZCY than the cobalt-containing conductor. The button cells of Ni–BZCY/BZCY/GBCuF were fabricated and tested from 500 to 700 °C with humidified H₂ (～3 % H₂O) as a fuel and ambient oxygen as the oxidant. A high open-circuit potential of 1.04 V, maximum power density of 414 mW cm^?2, and a low electrode polarization resistance of 0.21 Ω cm² were achieved at 700 °C, with calculated activation energy (E _a) of 128 kJ mol^?1 for the GBCuF cathode. The experimental results indicated that the layered perovskite GBCuF is a good candidate for cathode material.     

Synthesis and characterization of Ca and Sr co-doped ceria electrolytes

A series of Ce_0.85Ca_0.15?x Sr _x O_2–δ (x?=?0, 0.03 and 0.06) were synthesized via citrate–nitrate combustion method. Samples were first characterized by the X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD and SEM results showed that a complete solid solution formed in fluorite structure and Ce_0.85Ca_0.15?x Sr _x O_2?δ had homogeneous distribution of particle with grain size in the range of 2.5 to 3 μm. The electrical conductivities of Ce_0.85Ca_0.15?x Sr _x O_2?δ were evaluated for its use as a solid electrolyte in the intermediate-temperature solid oxide fuel cells by complex plane impedance measurements. Impedance measurements were made in the frequency range 1 MHz–0.1 Hz and temperature range 300–700 °C. It was found that Ce_0.85Ca_0.12Sr_0.03O_2?δ showed highest conductivity.     

Promising performances for a La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Co<Subscript>0.8</Subscript>Fe<Subscript>0.2</Subscript>O<Subscript>3-δ</Subscript> cathode with a dense interfacial layer at the electrode-electrolyte interface

As for the commonly studied La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (6428), here, a very low area-specific resistance (ASR) was measured for La_0.6Sr_0.4Co_0.8Fe_0.2O_3-δ (6482) cathode deposited on a Ce_0.9Gd_0.1O_2-δ (GDC) electrolyte with addition of a thin (1 μm) dense LSCF film deposited by spin coating at the interface between the GDC electrolyte and a 40-μm-thick screen-printed electrode. The ASR ranged from 1 Ω.cm² at 500 °C, 0.11 Ω.cm² at 625 °C and value as low as 0.03 Ω.cm² at 700 °C. Impedance spectra collected in between 500 and 700 °C were carefully studied. They could all be modelled with two R//CPE in series which are likely associated to the oxygen reduction reaction itself (dissociation/adsorption/ionization) at low frequency and to the oxide ion transfer at the electrode/electrolyte interface at high frequency.     

Microstructure and electrochemical properties of porous La2NiO4+δ electrodes spin-coated on Ce0.8Sm0.2O1.9 electrolyte

Porous La₂NiO_4+?? electrodes were prepared from superfine starting powder on dense substrates of Ce_0.8Sm_0.2O_1.9 electrolyte by a spin coating technique. The microstructure and electrochemical properties of the electrodes were investigated within the sintering temperature range of 1,000?C1,100?°C. An obvious effect of sintering temperature on the microstructure and electrochemical properties was detected. The variation of the electrochemical properties with sintering temperature was explained in relation to the microstructural evolution of the porous electrodes. It was detected that the electrode processes greatly depended on the microstructure of the electrodes. The polarization of surface oxygen exchange process was found to be the major contribution to the total electrode polarization. The electrode sintered at 1,050?°C showed the optimum electrocatalytic activity among the investigated electrodes. At 800?°C, the electrode exhibited a polarization resistance of 0.42????cm², an overpotential of 48?mV at a current density of 200?mA?cm^?2 and an exchange current density of 121?mA?cm^?2.     

Genesis,structural, and transport properties of La<Subscript>2</Subscript>Mo<Subscript>2-x</Subscript>W<Subscript>x</Subscript>O<Subscript>9</Subscript> prepared via mechanochemical activation

Fast oxide-ion conductors La₂Mo_2-xW_xO₉ (x = 0–1) have been prepared using mechanochemical activation (MA) of starting oxides in a high-power planetary ball mill. Studies of La₂Mo_2-xW_xO₉ genesis and structural properties using thermal analysis, XRD, SEM, IR, and Raman spectroscopy have revealed that MA results in the formation of an amorphous precursor, while the cubic β-phase is formed after calcination at 700–900 °C. Due to a high dispersion of powders, high-density pellets of W-LAMOX ceramics have been obtained already after sintering at 950 °C. Their electrical conductivity measured by the impedance spectroscopy depends on the W concentration being sufficiently high (up to 5.6?10^?3 S/cm at 630 °C) at temperatures below 650 °C.     

Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by substituting La3+ with Sm3+

The microwave dielectric properties of La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. Apparent density of 6.59 g/cm³, dielectric constant (ε_r) of 19.9, quality factor (Q×f) of 70,200 GHz, and temperature coefficient of resonant frequency (τ_f) of ?77 ppm/°C were obtained for La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h. The dielectric constant, and τ_f of La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics were almost independent with the sintering temperature as the sintering temperature varied from 1450 to 1600 °C.     

Fabrication of LSM-SDC composite cathodes for intermediate-temperature solid oxide fuel cells

Microstructure, interfacial resistance, and activation energy for composite cathodes consisting of 50 wt% (La_0.85Sr_0.15)_0.9MnO_3-δ (LSM) and 50 wt% Sm_0.2Ce_0.8O_1.90 (SDC) were studied for intermediate-temperature solid oxide fuel cells based on SDC electrolytes. Microstructure and interfacial resistance were greatly influenced by the characteristics of starting powder and temperatures sintering the electrodes. Optimum sintering temperatures were 1100 and 950 °C, respectively, for electrodes with SDC prepared using oxalate coprecipitation technique (OCP) and glycine-nitrate process (GNP). Area-specific resistances determined using impedance spectroscopy were 0.47 and 0.92 Ω cm² at 800 °C for LSM-SDC/OCP and LSM-SDC/GNP, respectively. The high electrochemical performance is attributed to small grain size, high porosity, and high in-plane electrical conductivity of composite cathode, demonstrating the dramatic effects of microstructure on electrode performance. To increase the electrode performance, it is critical to enhance the diffusion rate of oxygen species.     

Structural,thermal and electrical properties of Bi and Y co-doped barium zirconium cerates

Bismuth- and yttrium-co-doped barium cerates were successfully synthesised by solid-state reactions followed by sintering between 1,400 and 1,500 °C for 1 to 6 h allowing densification above 98 % to be obtained. All samples were found to retain their original orthorhombic structure after treatment in either oxidising or reducing atmospheres (dry and wet). Mechanical strength was affected by structure upon reduction due in part to strains and stresses induced by bismuth ionic size variations. Conductivity values as high as 0.055 S/cm were obtained for sample BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ and of 0.0094 S/cm for the Zr-free compound BaCe_0.7Y_0.2Bi_0.1O_3?δ at 700 °C in air. In all the investigated materials, sample BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ exhibits the highest conductivity in both air and wet 5 % H₂/Ar with good mechanical strength. BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ is a promising mixed H⁺/e^? conductor, a potential component of composite anode for solid oxide fuel cells.     

Synthesis and electric properties of perovskite Pr0.6Ca0.4Fe0.8Co0.2O3 for SOFC applications

In this study, polycrystalline powder Pr_0.6Ca_0.4Fe_0.8Co_0.2O₃ (PCFC) was synthesized by a sol–gel process. This oxide was analyzed by X-ray powder diffraction. Synthesized Pr_0.6Ca_0.4Fe_0.8Co_0.2O₃ showed up to be single phase and belongs to the orthorhombic crystalline system with a Pbnm space group. The microstructural features of the synthesized products display particles having an irregular morphology and a size in the range of 50–100 nm. X-ray diffraction (XRD) analysis shows the chemical compatibility between the PCFC cathode and the electrolyte Sm-doped ceria since no reaction products were honored when the material was mixed and co-fired at 1,000 °C for 168 h. The thermal expansion coefficient of PCFC 16.9?×?10^?6 °C^?1 is slightly higher than that of Ce_0.8Sm_0.2O_1.9 (SDC) over the studied temperature range. The greater contribution to the total resistance of the electrode is the electrochemical resistance associated with oxygen exchange in the cathode surface (0.96 Ωcm²). The dc four-probe measurement indicated that PCFC exhibits fairly high electrical conductivity, over 100 S cm^?1 at T?≥?500 °C, making this material promising as a cathode material for intermediate temperature solid oxide fuel cells.     

Effect of sintering aid MoO3 on the microstructure and ionic conductivity of ceria- and lanthanum gallate-based electrolytes

The effect of a small addition of MoO₃ on the microstructure and ionic conductivity of Nd_0.2Ce_0.8O_1.9 (NDC), La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (LSGM) and Nd_0.2Ce_0.8O_1.9-La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (NDC-LSGM) has been investigated. The microstructure and electrical properties of the samples were characterized by X-ray diffraction, field-emission scanning electron microscopy and electrochemical impedance spectroscopy. The results show that MoO₃ doping can obviously increase the densification and grain sizes, and decrease the grain and grain boundary resistances of the NDC, LSGM and NDC-LSGM electrolytes. It expands the oxygen ion channels and reduces the total conductance activation energy of the system. The total conductivities of MoO₃-doped NDC and NDC-LSGM samples are 1.56 and 2.10 times higher than that of the undoped NDC system at 450°C. The total conductivity of LSGM-Mo is 1.46 times higher than that of LSGM at 450°C. These finding suggest that MoO₃ is considered to be an effective sintering aid that optimizes the electrical properties of NDC, LSGM and NDC-LSGM electrolytes.     

Modification of B-site doping of perovskite LaxSr1 − xFe1 − y−zCoyCrzO3 − δ oxide by Mg2+ ion

Co-doping B-site of perovskite oxide La_xSr_1 ? xCo_yFe_1 ? yO_3 ? δ (LSCFO) with Cr⁶⁺ and Mg²⁺ ions has been attempted in this research for revamping chemical stability and oxygen ionic conductivity of this mixed conducting oxide. It is known that partial substitution for B-site cations of LSCFO by Cr gives rise to a significant improvement on chemical and thermal stability of the perovskite oxide. On the basis of this doped structure, introduction of an immaterial dose of Mg²⁺ ion into its B-site results in a microstructure consisting of smaller grains with higher density than its precursor. Furthermore, the resulting perovskite oxide La_0.19Sr_0.8Fe_0.69Co_0.1Cr_0.2 Mg_0.01O_3 ? δ (LSFCCMO) displays higher O^2? conductivity than the solely Cr-doped LSCFO besides the improved chemical stability against reduction in 5% CH₄/He stream at 850 °C. A detailed examination of the oxidation states of B-site transition metal ions by XPS has also been conducted as a part of structural characterizations of LSFCCMO. The assessment of relative O^2? conductivity shows that the grain boundary area plays a more important role than the bulk phase in facilitating ion transport, but with comparable boundary areas the higher densification level is favorable.     

Preparation of dense La<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>Ga<Subscript>0.8</Subscript>Mg<Subscript>0.2</Subscript>O<Subscript>3-δ</Subscript> with high ionic conductivity by solid-state synthesis

The results of a systematic investigation on the effects of processing steps, via solid-state reactions, on structural phase characteristics and ionic conductivity of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ solid electrolyte are reported. The main purpose of this work is to establish an optimized route for obtaining good densification and high ionic conductivity of this solid electrolyte. Processing routes with three successive calcinations at 1250 °C followed by attrition milling (R1), and with two sequences of calcination at 1350 °C with intermediary attrition milling (R2) give rise to near full density at 1450 °C sintering temperature. The rate of grain growth is fast when the relative density reaches 95%. Elemental mapping reveals uniform distribution of the constituents in the matrix along with La₄Ga₂O₉, LaSrGa₃O₇ and sub-micrometer MgO grains at grain boundaries. The ionic conductivity of grains remains unchanged with the processing route and sintering profile. The blocking effect of charge carriers at grain boundaries decreases with increasing the dwell temperature.     

La0.8Sr0.2Cr1 − xRuxO3 − δ–Gd0.1Ce0.9O1.95 solid oxide fuel cell anodes: Ru precipitation and electrochemical performance

Composites containing La_0.8Sr_0.2Cr_1 ? xRu_xO_3 ? δ (LSCrRu) with x = 0–0.25 and Gd_0.1Ce_0.9O_1.95 (GDC) were studied as anodes in solid oxide fuel cells (SOFCs) with La_0.9Sr_0.1Ga_0.8Mg_0.2O_3 ? δ (LSGM) electrolytes. Electrode polarization resistance R_P decreased during initial SOFC operation before reaching a minimum. The decrease was more rapid, and the ultimate R_P value reached was generally lower, with increasing temperature and Ru content x. R_P was stable at longer times except for x = 0.25 where it increased slightly. SOFCs with x = 0.18 anodes at 800 °C yielded power densities as high as 0.53 W/cm² with an R_P value, including the (La,Sr)(Co,Fe)O₃–GDC cathode, of < 0.15 Ω cm². Transmission electron microscopy revealed Ru nano-particles on LSCrRu surfaces; their size increased and their density decreased with increasing temperature. Increasing the Ru content increased the density of Ru surface particles at a given time and temperature. Measured early-stage Ru surface coverage values were consistent with a model where Ru supply to the LSCrRu surface was limited by Ru bulk out-diffusion, but the coverage saturated at longer times. There was surprisingly little Ru particle coarsening over times up to 1000 h at 800 °C, with Ru particles sizes remaining < 10 nm. The cell R_P values generally decreased with increasing Ru nano-particle surface area.     

Effect of lanthanum ions on magnetic properties of Y3Fe5O12 nanoparticles

Lanthanum ion (La³⁺)-substituted garnet nanoparticles Y_3?x La _x Fe₅O₁₂ (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) were fabricated by a sol–gel method. Their crystalline structures and magnetic properties were investigated by using X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and Mössbauer spectrum. The XRD results show that samples of Y_3?x La _x Fe₅O₁₂ (0.0 ≤ x ≤ 0.8) are all single phase and the sizes of particles range from 32 to 65 nm. Those of Y₂LaFe₅O₁₂ consisted of peaks from garnet and LaFeO₃ structures. Compared to pure YIG, the saturation magnetization is larger when the La concentration x = 0.2. However, with increasing La concentration (x), it decreases obviously. Meanwhile, may be due to the enhancement of the surface spin effects, the saturation magnetization rises as the particle size is increased. Different from the pure YIG, the Mössbauer spectra of Y_2.8La_0.2Fe₅O₁₂ and Y_2.2La_0.8Fe₅O₁₂ are composed of four sets of six-line hyperfine patterns. The results tell us that the substitution of La³⁺ ions with large ionic radius (1.061 Å) will give rise to a microscopic structure distortion of the a- and d-sites to different degrees, and the Zeeman sextets from a- and d-sites begin to split into two sub-sextets, which is helpful to explain the phenomenon observed in the study of the magnetic property.     

Synthesis and investigations on the stability of La0.8Sr0.2CuO2.4+δ at high temperatures

For application in solid oxide fuel cells La_0.8Sr_0.2CuO_2.4+δ was synthesized and the phase evolution was characterized after quenching from different temperatures and after slow cooling. A single phase perovskite was found after quenching from 950 °C. The electrical conductivity of the La_0.8Sr_0.2CuO_2.4+δ perovskite exhibited metallic behavior reaching values of about 270 S/cm at 800 °C in air. The thermal expansion between 30 and 800 °C gave a thermal expansion coefficient of 11.1 × 10^− 6 K^− 1.At higher temperatures, the perovskite was transformed to the K₂NiF₄-type structure via an intermediate stage that can be best described as a LaSrCuO₄ phase with preferential growing of {020} lattice planes. After sintering at 1100 °C and slow cooling in the furnace a phase mixture of (La,Sr)CuO_4+δ and (La,Sr)CuO_2.4+δ perovskite was obtained. This phase mixture showed higher electrical conductivity (400 S/cm at 800 °C) and smaller thermal expansion coefficient (9.6 × 10^− 6 K^− 1) than the single phase La_0.8Sr_0.2CuO_2.4+δ perovskite.