Impact of Silica Additions on the Phase Composition and Electrical Transport Properties of Ruddlesden-Popper La2NiO4+δ Mixed Conducting Ceramics

The present work explores the possibility of incorporation of silicon into the crystal structure of Ruddlesden-Popper La2NiO4+δ mixed conducting ceramics with the aim to improve the chemical compatibility with lanthanum silicate-based solid electrolytes. Ceramics with the nominal composition La2Ni1−ySiyO4+δ (y = 0, 0.02 and 0.05) were prepared by the glycine nitrate combustion technique and sintered at 1450 °C. While minor changes in the lattice parameters of the tetragonal K2NiF4-type lattice may suggest incorporation of a small fraction of Si into the Ni sublattice, combined XRD and SEM/EDS studies indicate that this fraction is very limited (≪2 at.%, if any). Instead, additions of silica result in segregation of apatite-type La10−xSi6O26+δ and La2O3 secondary phases as confirmed experimentally and supported by the static lattice simulations. Both total electrical conductivity and oxygen-ionic transport in La2NiO4+δ ceramics are suppressed by silica additions. The preferential reactivity of silica with lanthanum oxide opens a possibility to improve the compatibility between lanthanum silicate-based solid electrolytes and La2NiO4+δ-based electrodes by appropriate surface modifications. The promising potential of this approach is supported by preliminary tests of electrodes infiltrated with lanthanum oxide.

Formation of Solid Solutions and Physicochemical Properties of the High-Entropy Ln1−xSrx(Co,Cr,Fe,Mn,Ni)O3−δ (Ln = La, Pr, Nd, Sm or Gd) Perovskites

Phase composition, crystal structure, and selected physicochemical properties of the high entropy Ln(Co,Cr,Fe,Mn,Ni)O3−δ (Ln = La, Pr, Gd, Nd, Sm) perovskites, as well as the possibility of Sr doping in Ln1−xSrx(Co,Cr,Fe,Mn,Ni)O3−δ series, are reported is this work. With the use of the Pechini method, all undoped compositions are successfully synthesized. The samples exhibit distorted, orthorhombic or rhombohedral crystal structure, and a linear correlation is observed between the ionic radius of Ln and the value of the quasi-cubic perovskite lattice constant. The oxides show moderate thermal expansion, with a lack of visible contribution from the chemical expansion effect. Temperature-dependent values of the total electrical conductivity are reported, and the observed behavior appears distinctive from that of non-high entropy transition metal-based perovskites, beyond the expectations based on the rule-of-mixtures. In terms of formation of solid solutions in Sr-doped Ln1−xSrx(Co,Cr,Fe,Mn,Ni)O3−δ materials, the results indicate a strong influence of the Ln radius, and while for La-based series the Sr solubility limit is at the level of xmax = 0.3, for the smaller Pr it is equal to just 0.1. In the case of Nd-, Sm- and Gd-based materials, even for the xSr = 0.1, the formation of secondary phases is observed on the SEM + EDS images.

Structure and Electrical Properties of Superionic Ceramics Based on Silver-Enriched (Cu0.25Ag0.75)7SiS5I Solid Solution

(Cu0.25Ag0.75)7SiS5I-based superionic ceramics were fabricated by using the micro- and nanopowders. The XRD technique and microstructural analysis are applied for the structural studies of powders and ceramic samples. The impedance measurements of ceramic samples are carried out in the frequency range from 10Hz to 2 × 106 Hz and temperature interval from 292 K to 383 K. The contributions of ionic and electronic conductivities into the total electrical conductivity are determined, and their temperature dependences are investigated. The influence of the size effect on ionic and electronic conductivities and their activation energies in (Cu0.25Ag0.75)7SiS5I-based ceramics is studied.

Impact of Praseodymia Additions and Firing Conditions on Structural and Electrical Transport Properties of 5 mol.% Yttria Partially Stabilized Zirconia (5YSZ)

Ceramics samples with the nominal composition [(ZrO2)0.95(Y2O3)0.05]1-x[PrOy]x and praseodymia contents of x = 0.05–0.15 were prepared by the direct firing of compacted 5YSZ + PrOy mixtures at 1450–1550 °C for 1–9 h and characterized for prospective applicability in reversible solid oxide cells. XRD and SEM/EDS analysis revealed that the dissolution of praseodymium oxide in 5YSZ occurs via the formation of pyrochlore-type Pr2Zr2O7 intermediate. Increasing PrOy additions results in a larger fraction of low-conducting pyrochlore phase and larger porosity, which limit the total electrical conductivity to 2.0–4.6 S/m at 900 °C and 0.28–0.68 S/m at 700 °C in air. A longer time and higher temperature of firing promotes the phase and microstructural homogenization of the ceramics but with comparatively low effect on density and conductivity. High-temperature processing leads to the prevailing 3+ oxidation state of praseodymium cations in fluorite and pyrochlore structures. The fraction of Pr4+ at 600–1000 °C in air is ≤2% and is nearly independent of temperature. 5YSZ ceramics with praseodymia additions remain predominantly oxygen ionic conductors, with p-type electronic contribution increasing with Pr content but not exceeding 2% for x = 0.15 at 700–900 °C. The average thermal expansion coefficients of prepared ceramics are in the range of 10.4–10.7 ppm/K.

Influence of cation substitution on electrical conductivity of microcrystalline ceramics based on (Cu1-xAgx)7GeSe5I solid solutions

Ceramic samples based on the microcrystalline powders (Cu1–хAgx)7GeSe5I (x = 0, 0.25, 0.5, 0.75, 1) were prepared by pressing them at the pressure close to 400 MPa and subsequent annealing at 873 K for 36 hours. Using the microstructural analysis, the average size of microcrystallites of these samples was determined. Investigation of electrical conductivity of ceramics based on (Cu1 хAgx)7GeSe5I solid solutions was carried out using the method of impedance spectroscopy in the frequency range from 10 Hz to 3×105 Hz and within the temperature range 293...383 K. Analysis of the Nyquist plots allowed determining the contributions of ionic and electronic components to the total electrical conductivity. The temperature dependence of ionic and electronic conductivity in Arrhenius coordinates is linear, which indicates their thermoactivation character. The compositional behaviour of ionic and electronic conductivity, as well as their activation energies have been studied. Their nonlinear character can be explained by the complex process of recrystallization and Cu+ ↔ Ag+ cation substitution within the cationic sublattice.

DC 4-Point Measurement for Total Electrical Conductivity of SOFC Cathode Material

Conductive oxides are widely studied as cathode materials for electrochemical cells, such as solid oxide fuel cells (SOFCs), because of their chemical stability and high electrical conductivity at high temperatures (800–950 °C). The cathode is a key component of SOFCs, accounting for the greatest resistance loss among the SOFC components. It is important to precisely determine the conductivity of the cathode material, but it is difficult to achieve consistency among measurements because of errors caused by differences in the measurement methods and conditions employed by various research teams. In this study, the total electrical conductivity of an SOFC cathode material was measured by the DC 4-point method by investigating the geometrical parameters of the sample and the measurement terminal and the measurement device using La0.8Sr0.2MnO3+d (LSM). The measurement variables included the spacing between the measurement terminals (1 and 2 cm), lead wire diameter (0.25 and 0.5 mm), specimen thickness (3, 4, and 5 mm), and the applied current (10, 50, and 100 mA). The larger the spacing between the measurement terminal and the thinner the specimen, the smaller the standard deviation.

Changes on the Surface of the SiO2/C Composite, Leading to the Formation of Conductive Carbon Structures with Complex Nature of DC Conductivity

Sol–gel layers have been the subject of many studies in recent decades. However, very little information exists about layers in which carbon structures are developed in situ. Using the spin-coating method, we obtained thin iron-doped SiO2/C composite films. The results of Raman spectroscopy showed that our samples consisted of graphitic forms and polymers. The latter’s contribution decreases with rising temperature. FTIR and EDS studies show changes in carbon distribution on top of the layer, depending on the sintering temperature. The samples sintered at 800 °C showed a significant increase in the contribution of carbon forms to the layer’s surface. Therefore, high conductivity can be observed in this sample. The results of XPS spectroscopy showed that the contribution of sp3 hybridized carbon increases after etching. The total electrical conductivity, studied by a DC four-wire technique, increased with the temperature and showed almost linear characteristics with significant changes below 150 K. The reduced activation energy plot has a positive temperature coefficient, which is a characteristic property of the conductive polymers in a metallic regime of conductivity.

New Good Ionic Conductor: Ba-Deficient Ba3Y4O9 with Zr Substitution

<p>To lower operating temperatures of solid oxide fuel cells (SOFCs), the development of ion-conducting oxides with high conductivity and durability is desired. In this work, we investigated Zr-substituted “Ba₃Y₄O₉” as an ionic conductor at intermediate temperatures and found that the Zr substitution for Y dramatically improves the phase stability in humidified atmospheres at 300-800 °C. The total electrical conductivity of 20 mol% Zr-substituted Ba₃Y₄O₉ is about 1 mS/cm at 700 °C in dry H­₂ and O₂ atmospheres and the contribution of electronic conduction (both hole and electron) is relatively small compared with Y-doped BaZrO₃ (BZY) and Gd-doped CeO­­₂ (GDC) which are typical intermediate-temperature ionic conductors. Besides, in the Zr-substituted “Ba₃Y₄O₉” samples, we observed that BaO-rich amorphous phase coexists with the main phase whose composition is estimated to be Ba:(Y+Zr) ~ 2:3. Therefore, the main conducting phase might be Ba-deficient Ba₃Y₄O₉. The mechanism of the ionic conduction and the improvement of chemical stability has not been revealed yet due to the lack of crystallographic information about the Ba-deficient phase. While we are now working on further investigation, we promptly report the characteristic of the new compound.</p>

New Good Ionic Conductor: Ba-Deficient Ba3Y4O9 with Zr Substitution

<p>To lower operating temperatures of solid oxide fuel cells (SOFCs), the development of ion-conducting oxides with high conductivity and durability is desired. In this work, we investigated Zr-substituted “Ba₃Y₄O₉” as an ionic conductor at intermediate temperatures and found that the Zr substitution for Y dramatically improves the phase stability in humidified atmospheres at 300-800 °C. The total electrical conductivity of 20 mol% Zr-substituted Ba₃Y₄O₉ is about 1 mS/cm at 700 °C in dry H­₂ and O₂ atmospheres and the contribution of electronic conduction (both hole and electron) is relatively small compared with Y-doped BaZrO₃ (BZY) and Gd-doped CeO­­₂ (GDC) which are typical intermediate-temperature ionic conductors. Besides, in the Zr-substituted “Ba₃Y₄O₉” samples, we observed that BaO-rich amorphous phase coexists with the main phase whose composition is estimated to be Ba:(Y+Zr) ~ 2:3. Therefore, the main conducting phase might be Ba-deficient Ba₃Y₄O₉. The mechanism of the ionic conduction and the improvement of chemical stability has not been revealed yet due to the lack of crystallographic information about the Ba-deficient phase. While we are now working on further investigation, we promptly report the characteristic of the new compound.</p>

Designing and Synthesis of (Cd2+, Li+), Cr3+, Bi3+ Doped CePO4 Materials Optical, Electrochemical, Ionic Conductivity Analysis

Most of the work has been done on the optical properties of the rare earth doped CePO4, so there are few studies on the effect of metal ion doping on CePO4. The doping improves the properties of the compounds and can lead to new properties. It is the first time, that multi- ionic doping process is used in the CePO4matrix, in order to improve the ionic conductivity and the electrochemical stability. The low percentage of (Cd2+, Li+), Cr3+, Bi3+ dopant affect the structure showing a weak decrease in the lattice parameters compared to the CePO4. Impedance spectroscopy analysis was used to analyze the electrical behavior of samples as a function of frequency at different temperatures. The total electrical conductivity plots obtained from impedance spectra shows an increase of the total conductivity as Li, Cr-content increases. The determined energy gap values decrease with increasingly Li+, Cr3+ and Bi3+ doping content. Electrochemical tests showed an improved capacity when increasing the Li+, Cr3+ and Bi3+ content and a stable cycling performance.