High Oxide Ion Conductivity Research Articles

High oxygen vacancy concentration and improved electrical conductivity in tetragonal LaNbO4 stabilized by Ga and Mo Co-doping on the Nb site

The LaNbO4-based materials were well documented to be good ionic conductors with the charge carriers of protons or interstitial oxygen ions. Herein, for the first time, we reported that the high oxide ion conduction, e.g. 3 × 10−3 S cm−1 at 900 °C, mediated by oxygen vacancies was achieved in LaNbO4 via equimolar Ga and Mo co-doping on the Nb site. Such a co-doping effectively stabilize the high temperature tetragonal structure of LaNbO4 to room temperature, and thus represents the first case of room temperature tetragonal LaNbO4 with high oxygen vacancy concentration, in contrast with the previously reported tetragonal LaNbO4 stabilized by isovalent doping free of oxygen vacancies or donor-doping with interstitial oxygen. The local structure and conducting mechanism of oxygen vacancy defects were thoroughly studied by computational simulations. The results revealed that the oxygen vacancy was accommodated by transforming two neighboring isolated NbO4 tetrahedrons into a corner-sharing Nb2O7 unit, and the oxygen ion migrated via a cooperative process involving the breaking and reforming of Nb2O7 units, assisted by synergic rotation and deformation of other neighboring NbO4 tetrahedra. These findings provided us a more comprehensive understanding for the LaNbO4-based materials and emphasized the possibility of developing LaNbO4 material as oxide-ion conductors mediated by high concentration of oxygen vacancies.

Phases, stabilities, and oxide ion conductions of multiple lanthanide and tungsten co–doped δ-Bi2O3-based materials: From low to high configuration entropy

In this work, a series of multiple lanthanide and tungsten co-doped fluorite structured (Bi2O3)0.95-x(Ho0.4Er0.4Tm0.4Yb0.4Lu0.4O3)x(WO3)0.05 (x = 0.1, 0.2, 0.3, 0.4) and (Bi2O3)0.26(Ho0.5Er0.5Tm0.5Yb0.5O3)0.48(WO3)0.26 materials were prepared by traditional solid-state reaction method. The phases, stabilities, and electrical properties of these materials were thoroughly studied. The results revealed that under high oxygen partial pressure, CO2, or inert atmospheres, all these samples had excellent long term thermal stability and chemical stability, and the samples of (Bi2O3)0.95-x(Ho0.4Er0.4Tm0.4Yb0.4Lu0.4O3)x(WO3)0.05 (x = 0.1, 0.2, 0.3, 0.4) with low or mediate configuration entropies showed pure and high oxide ion conductivities, e.g. ∼2.6 × 10−2 S/cm at 600 °C for the sample x = 0.2. Whereas, for the (Bi2O3)0.26(Ho0.5Er0.5Tm0.5Yb0.5O3)0.48(WO3)0.26 sample with high configuration entropy, pure ionic conduction occurred only within a narrow temperature range (700−750 °C) under the N2 atmosphere. Under strong reducing condition, only the high-entropy sample (Bi2O3)0.26(Ho0.5Er0.5Tm0.5Yb0.5O3)0.48(WO3)0.26 showed high phase and chemical stabilities, but would introduce strong electronic conduction rise from the reduction of the high content W6+. While for (Bi2O3)0.95-x(Ho0.4Er0.4Tm0.4Yb0.4Lu0.4O3)x(WO3)0.05 with low or mediate configuration, phase decompositions with impurities of Bi metal and HoH2 were observed under strong reducing atmosphere, accompany with obviously decreased conductivities. Therefore, we provided here a comprehensive understanding for the multiple components doped Bi2O3-based materials with configuration entropy from low to high on their phases, stabilities, and electrical properties, and suggested a new strategy for designing and stabilizing bismuth-oxide-based materials.

High Conductivity and Diffusion Mechanism of Oxide Ions in Triple Fluorite-Like Layers of Oxyhalides.

Oxide ion conductors are attractive materials because of their wide range of applications, such as solid oxide fuel cells. Oxide ion conduction in oxyhalides (compounds containing both oxide ions and halide ions) is rare. In the present work, we found that Sillén oxychlorides, Bi2-xTexLuO4+x/2Cl (x = 0, 0.1, and 0.2), show high oxide ion conductivity. The bulk conductivity of Bi1.9Te0.1LuO4.05Cl reaches 10-2 S cm-1 at 431 °C, which is much lower than 644 °C of yttria-stabilized zirconia (YSZ) and 534 °C of La0.8Sr0.2Ga0.83Mg0.17O2.815 (LSGM). Thanks to the low activation energy, Bi1.9Te0.1LuO4.05Cl exhibits a high bulk conductivity of 1.5 × 10-3 S cm-1 even at a low temperature of 310 °C, which is 204 times higher than that of YSZ. The low activation energy is attributed to the interstitialcy oxide ion diffusion in the triple fluorite-like layer, as evidenced by neutron diffraction experiments (Rietveld and neutron scattering length density analyses), bond valence-based energy calculations, static DFT calculations, and ab initio molecular dynamics simulations. The electrical conductivity of Bi1.9Te0.1LuO4.05Cl is almost independent of the oxygen partial pressure from 10-18 to 10-4 atm at 431 °C, indicating the electrolyte domain. Bi1.9Te0.1LuO4.05Cl also exhibits high chemical stability under a CO2 flow and ambient air at 400 °C. The oxide ion conduction due to the two-dimensional interstitialcy diffusion is considered to be common in Sillén oxyhalides with triple fluorite-like layers, such as Bi1.9Te0.1RO4.05Cl (R = La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu) and Bi6-2xTe2xO8+xBr2 (x = 0.1, 0.5). The present study opens a new field of materials chemistry: oxide ion-conducting Sillén oxyhalides with triple fluorite-like layers.

Surface oxide ion conduction of BaCe0.5Pr0.3Y0.2O3−δ thin film with complex mixed valence states

Solid oxide fuel cells (SOFCs), which operate in the medium temperature range from 300 °C to 500 °C, are effective in shortening startup time and reducing fuel gas. In order to realize a practical electrolyte with high oxide ion conductivity, we have investigated the ionic conductivity of c-axis oriented BaCe0.5Pr0.3Y0.2O3−δ (BCPY) thin films with complex mixed valence states prepared on Al2O3 (0001) substrates by RF magnetron sputtering. The amount of oxygen vacancies on the surface in the as-deposited BCPY thin film was evaluated to be ∼6.7% by X-ray absorption spectroscopy and defect chemical analysis. The as-deposited film exhibited relatively high ionic conductivity (σT) of more than 10−1 S·K cm−1 and activation energy (E A) of ∼0.57 eV in the medium temperature range by thermal activation process on the surface. The energy separation between the top of the VB and the Fermi level was much larger than E A, indicating that the BCPY thin film is a pure oxide ion conductor without the contribution of electron or hole carriers. These results indicate that the c-axis oriented BCPY thin film can be applied to electrolyte of SOFC operating in the medium temperature range.

Machine Learning Combined with Weighted Voting Regression and Proactive Searching Progress to Discover ABO3-δ Perovskites with High Oxide Ionic Conductivity

Machine Learning Combined with Weighted Voting Regression and Proactive Searching Progress to Discover ABO_3-δ Perovskites with High Oxide Ionic Conductivity

Thermally Induced Oxygen Vacancies and High Oxide Ion Conduction in K2ZnV2O7 with a Melilite-Related Structure

Thermally Induced Oxygen Vacancies and High Oxide Ion Conduction in K₂ZnV₂O₇ with a Melilite-Related Structure

Preparation and characterization of La1.75Y0.25Mo2-xAlxO9-δ as solid electrolyte for intermediate temperatures SOFC

Yttrium and aluminium co-substitutions on lanthanum molybdate ceramics with the nominal formula La1.75Y0.25Mo2-xAlxO9-?? (LYMA, x = 0, 0.1, 0.2, 0.3 and 0.4) were synthesized by citric acid-nitrate combustion method and used for preparation of solid electrolyte for intermediate-temperature solid oxide fuel cells (ITSOFCs). Phase composition, structure, conductivity and electrical properties of LYMA have been investigated as a function of aluminium content by X-ray diffraction, scanning electron microscopy and electrochemical impedance spectroscopy, respectively. Experimental results showed that the substitution of La and Mo with appropriate amounts of Y and Al can effectively stabilize the ?-form of La2Mo2O9 at room temperature and inhibit its phase transition to ?-form. The LYMA synthesized by combustion method exhibited a better sinterability where relative density of the samples sintered at 950?C for 4 h was higher than 95%TD. The performance of the LYMA electrolyte was found to be related to Al-content. The La1.75Y0.25Mo1.8Al0.2O8.7 exhibited high oxide ion conductivity (?= 42mS/cm at 800?C) and low electrical activation energy (Ea = 1.18 eV). These preliminary results indicate that the LYMA is a promising electrolyte for IT-SOFCs.

Electrical and Dielectric Properties of Ca-Doped Bi-Deficient Sodium Bismuth Titanate Na0.5Bi0.49−xCaxTiO3−δ (0 ≤ x ≤ 0.08)

Bismuth-deficient sodium bismuth titanate (nominal Na0.5Bi0.49TiO2.985, NB0.49T) presents high oxide ion conductivity, which makes it a potential electrolyte material for intermediate-temperature solid oxide fuel cells. Acceptor doping has been proven an effective approach to enhance the bulk conductivity (σb) of NB0.49T. Here, divalent Ca2+ ions were selected to partially replace Bi3+ on the A-site of NB0.49T, and the temperature and composition dependences of σb and permittivity were investigated. Results showed that Ca2+ doping was effective for enhancing σb of NB0.49T by creating oxygen vacancies. The highest σb (0.006 S·cm−1 at 500 °C) was achieved by 2% Ca2+ doping. Further increase in the doping level decreased σb, which was more pronounced at temperatures below ~350 °C. Most importantly, Ca doping increased the temperature at which the activation energy for bulk conduction changed from ~0.80 eV (at low temperatures) to ~0.40 eV (at high temperatures), and reduced the temperature dependence of permittivity of NB0.49T. Results from the average structural parameters and the local defect associates are discussed. The findings of this work are helpful for understanding the defect and conduction mechanisms for acceptor-doped NB0.49T, and are also useful for developing NBT-based dielectrics with temperature-independent permittivity.

Preparation and Properties of Ce0.8Sm0.16Y0.03Gd0.01O1.9-BaIn0.3Ti0.7O2.85 Composite Electrolyte

Samarium, gadolinium, and yttrium co-doped ceria (Ce0.8Sm0.16Y0.03Gd0.01O1.9, CSYG) and BaIn0.3Ti0.7O2.85 (BIT07) powders were prepared by sol-gel and solid-state reaction methods, respectively. CSYG-BIT07 composite materials were obtained by mechanically mixing the two powders in different ratios and calcining at 1300 °C for 5 h. Samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), as well as electrical properties and thermal expansion coefficient (TEC) measurements. A series of CSYG-BIT07 composite materials with relative densities higher than 95% were fabricated by sintering at 1300 °C for 5 h. The performance of the CSYG-BIT07 composite electrolyte was found to be related to the content of BIT07. The CSYG-15% BIT07 composite exhibited high oxide ion conductivity (σ800°C = 0.0126 S·cm−1 at 800 °C), moderate thermal expansion (TEC = 9.13 × 10−6/K between room temperature and 800 °C), and low electrical activation energy (Ea = 0.89 eV). These preliminary results indicate that the CSYG-BIT07 material is a promising electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs).

Simultaneous Reduction of Proton Conductivity and Enhancement of Oxide-Ion Conductivity by Aliovalent Doping in Ba7Nb4MoO20.

Hexagonal perovskite-related oxides have garnered a great deal of research interest because of their high oxide-ion conductivity at intermediate temperatures, with Ba7Nb4MoO20 being a notable example. However, concomitant proton conduction in Ba7Nb4MoO20 may cause a decrease in power efficiency when used as the electrolyte in conventional solid oxide fuel cells. Here, through investigations of the transport and structural properties of Ba7Nb4-xWxMoO20+x/2 (x = 0-0.25), we show that the aliovalent substitution of Nb5+ by W6+ not only increases the oxide-ion conductivity but also dramatically lowers proton conductivity. The highest conductivity is achieved for x = 0.15 composition, with 2.2 × 10-2 S cm-1 at 600 °C, 2.2 times higher than that of pristine Ba7Nb4MoO20. The proton transport number of Ba7Nb3.85W0.15MoO20.075 is smaller compared with Ba7Nb4MoO20, Ba7Nb3.9Mo1.1O20.05, and Ba7Ta3.7Mo1.3O20.15. The structure analyses of neutron diffraction data of Ba7Nb3.85W0.15MoO20.075 at 25 and 800 °C reveal that the aliovalent W6+ doping introduces interstitial oxide ions in the intrinsically oxygen-deficient c' layers, thereby simultaneously increasing the carrier concentration for oxide-ion conduction and decreasing oxygen vacancies responsible for dissociative absorption of water. Neutron scattering length density distribution was examined using the maximum-entropy method and neutron diffraction data at 800 °C, which indicates the interstitialcy oxide-ion diffusion in the c' layers of Ba7Nb3.85W0.15MoO20.075. Ba7Nb3.85W0.15MoO20.075 exhibits extremely high chemical and electrical stability in the wide oxygen partial pressure P(O2) region [ex. 10-23 ≤ P(O2) ≤ 1 atm at 903 °C]. The present results offer a strategy for developing pure oxide-ion conducting hexagonal perovskite-related oxides for possible industrial applications.

On the mechanism of Mn(II)-doping in Scandia stabilized zirconia electrolytes

Cubic Scandia-stabilized zirconia (ScSZ) is an attractive electrolyte material for solid oxide cells due to its significant ionic conductivity, provided that the phase transition to its rhombohedral polymorph upon cooling is suppressed. The latter is achieved with addition of a secondary co-dopant, albeit it may be at the detriment of its ionic conductivity Here, we thoroughly investigate how MnO2 (0.5–10 mol%) as a co-dopant impacts on the sinterability, thermal expansion, crystal structure and ionic conductivity of ZrO2 doped with 10 mol% Scandia (10ScSZ), and we provide new insight on the chemistry of dissolved manganese in the fluorite lattice. Reactive sintering of 2 mol% MnO2 mixed with 10ScSZ enables to produce dense electrolyte with significant reduction of the peak sintering temperature and stabilisation of the cubic structure down to room temperature. Combined density functional theory and X-ray photoelectron spectroscopy analyses reveal that manganese predominantly enters the structure as Mn2+ during reactive sintering, with a prevalence of higher valence states at the surface and grain boundaries. The highest oxide ion conductivity is achieved for 2 mol% doped 10ScSZ (120 mScm−1 at 800 °C) and it decreases with increasing Mn concentration. For all compositions, the bulk conductivity remains independent of pO2 – corroborating a limited electronic conductivity contribution from Mn-doping. The grain boundary conductivity is found to decrease with sintering time and pO2, which is attributed to the chemistry and concentration of segregated manganese at the surface and grain boundaries, yielding depletion of oxygen vacancies in the space charge layer.

Gd3+ and Bi3+ co-substituted cubic zirconia; (Zr1-x-y Gd x Bi y O2-δ ): a novel high κ relaxor dielectric and superior oxide-ion conductor.

Solid oxide fuel cells (SOFCs) offer several advantages over lower temperature polymeric membrane fuels cells (PMFCs) due to their multiple fuel flexibility and requirement of low purity hydrogen. In order to decrease the operating temperature of SOFCs and to overcome the high operating cost and materials degradation challenges, the Cubic phase of ZrO2 was stabilized with simultaneous substitution of Bi and Gd and the effect of co-doping on the oxide-ion conductivity of Zr1−x−yBixGdyO2−δ was studied to develop a superior electrolyte separator for SOFCs. Up to 30% Gd and 20% Bi were simultaneously substituted in the cubic ZrO2 lattice (Zr1−x−yGdxBiyO2−δ, x + y ≤ 0.4, x ≤ 0.3 and y ≤ 0.2) by employing a solution combustion method followed by multiple calcinations at 900 °C. Phase purity and composition of the material is confirmed by powder XRD and EDX measurements. The formation of an oxygen vacant Gd/Bi co-doped cubic zirconia lattice was also confirmed by Raman spectroscopy study. With the incorporation of Bi3+ and Gd3+ ions, the cubic Zr1−x−yBixGdyO2−δ phase showed relaxor type high κ dielectric behaviour (ε′ = 9725 at 600 °C at applied frequency 20 kHz for Zr0.6Bi0.2Gd0.2O1.8) with Tm approaching 600 °C. The high polarizability of the Bi3+ ion coupled with synergistic interaction of Bi and Gd in the host ZrO2 lattice seems to create the more labile oxide ion vacancies that enable superior oxide-ion transport resulting in high oxide ion conductivity (σo > 10−2 S cm−1, T > 500 °C for Zr0.6Bi0.2Gd0.2O1.8) at relatively lower temperatures.

Ruddlesden–Popper Oxychlorides Ba3Y2O5Cl2, Sr3Sc2O5Cl2, and Sr2ScO3Cl: First Examples of Oxide-Ion-Conducting Oxychlorides

Oxide-ion conductors are attractive materials due to their wide applications such as solid oxide fuel cells (SOFCs). Crucial to the developments of the applications is the discovery of a class of oxide-ion conductors. Some Ruddlesden–Popper (RP) oxychlorides are expected to show high oxide-ion conductivity, because they have larger free and lattice volumes than RP oxides, leading to low activation energies. Here, we discover RP oxychlorides Ba3Y2O5Cl2, Sr3Sc2O5Cl2, and Sr2ScO3Cl as a class of oxide-ion conductors. Rietveld analyses of X-ray powder diffraction data indicate that Ba3Y2O5Cl2 and Sr3Sc2O5Cl2 are tetragonal I4/mmm n = 2 RP phases and that Sr2ScO3Cl is a tetragonal P4/nmm n = 1 RP phase. The predominant conducting species in Ba3Y2O5Cl2, Sr3Sc2O5Cl2, and Sr2ScO3Cl is strongly suggested to be the oxide ion by (i) direct-current (DC) polarization measurements, (ii) electrolyte domains observed in the oxygen partial pressure dependence of DC electrical conductivities at constant temperatures, and (iii) wide optical band gaps. DFT calculations of Ba3Y2O5Cl2 show a lower energy barrier for oxide-ion migration than that for chloride-ion migration, which supports the oxide-ion conduction. The DFT results indicate that oxide ions in Ba3Y2O5Cl2 two-dimensionally migrate mainly through equatorial oxygen O1 sites along the O1–O1 edge of the YO5 square pyramid. The oxide-ion conductivity of Ba3Y2O5Cl2 is considerably higher than that of Sr3Sc2O5Cl2, mainly due to a lower activation energy for conductivity, which can be ascribed to the larger free and lattice volumes of Ba3Y2O5Cl2. The DFT energy barrier for oxide-ion migration and experimental activation energy for bulk conductivity in Ba3Y2O5Cl2 are as low as those of a leading oxide-ion conductor La0.9Sr0.1Ga0.95Mg0.05O3−δ. Thus, the present work suggests that RP oxychlorides are a class of potential oxide-ion conductors.

High Oxide-Ion Conductivity in a Hexagonal Perovskite-Related Oxide Ba7 Ta3.7 Mo1.3 O20.15 with Cation Site Preference and Interstitial Oxide Ions.

Solid oxide-ion conductors are crucial for enabling clean and efficient energy devices such as solid oxide fuel cells. Hexagonal perovskite-related oxides have been placed at the forefront of high-performance oxide-ion conductors, with Ba7 Nb4- x Mo1+ x O20+ x /2 (x= 0-0.1) being an archetypal example. Herein, high oxide-ion conductivity and stability under reducing conditions in Ba7 Ta3.7 Mo1.3 O20.15 are reported by investigating the solid solutions Ba7 Ta4- x Mo1+ x O20+ x /2 (x= 0.2-0.7). Neutron diffraction indicates a large number of interstitial oxide ions in Ba7 Ta3.7 Mo1.3 O20.15 , leading to a high level of oxide-ion conductivity (e.g., 1.08 × 10-3 S cm-1 at 377 °C). The conductivity of Ba7 Ta3.7 Mo1.3 O20.15 is higher than that of Ba7 Nb4 MoO20 and conventional yttria-stabilized zirconia. In contrast to Ba7 Nb4- x Mo1+ x O20+ x /2 (x= 0-0.1), the oxide-ion conduction in Ba7 Ta3.7 Mo1.3 O20.15 is dominant even in highly reducing atmospheres (e.g., oxygen partial pressure of 1.6 × 10-24 atm at 909°C). From structural analyses of the synchrotron X-ray diffraction data for Ba7 Ta3.7 Mo1.3 O20.15 , contrasting X-ray scattering powers of Ta5+ and Mo6+ allow identification of the preferential occupation of Mo6+ adjacent to the intrinsically oxygen-deficient layers, as supported by DFT calculations. The high conductivity and chemical and electrical stability in Ba7 Ta3.7 Mo1.3 O20.15 provide a strategy for the development of solid electrolytes based on hexagonal perovskite-related oxides.

Facile and reproducible method of stabilizing hbox {Bi}_2hbox {O}_3 phases confined in nanocrystallites embedded in amorphous matrix

Bismuth sesquioxide (hbox {Bi}_2hbox {O}_3) draws much attention due to wide variety of phases in which it exists depending on the temperature. Among them, delta phase is specially interesting because of its high oxide ion conductivity and prospects of applications as an electrolyte in fuel cells. Unfortunately, it is stable only in a narrow temperature range ca. 730–830 ^{circ }C. Our group has developed a facile and reproducible two-stage method of stabilizing hbox {Bi}_2hbox {O}_3 crystalline phases confined in nanocrystallites embedded in amorphous matrix. In the first stage, glassy materials were obtained by a routine melt-quenching method: pure hbox {Bi}_2hbox {O}_3 powders were melted in porcelain crucibles and fast-cooled down to room temperature. In the second step, the materials were appropriately heat-treated to induce formation of crystallites of beta, delta or gammahbox {Bi}_2hbox {O}_3 phases confined in a glassy matrix, depending on the process conditions. It was found out that the vitrification of the initial hbox {Bi}_2hbox {O}_3 and the subsequent nanocrystallization were unexpectedly possible due to the presence of some Al, and Si impurities from the crucibles. Systematic DTA, XRD, optical, Raman and SEM/EDS studies were carried out to investigate the influence of the syntheses processes and allowed us to determine conditions under which the particular phases appear and remain stable down to room temperature.

Associating High Oxide-Ion Conductivity and Conduction Mechanisms with Local Atomic Environments in Na0.5Bi0.5–xTi1–yMgyO3−δ

Associating High Oxide-Ion Conductivity and Conduction Mechanisms with Local Atomic Environments in Na_0.5Bi_{0.5–<i>x</i>}Ti_1–<i>y</i>Mg_<i>y</i>O_3−δ

Oxygen migration in doped BaGdInO4

Doped-BaGdInO4 is a promising material for many applications including solid oxide fuel cells due to its high oxide-ion conductivity. Here we employ atomistic simulations to show that the activation energy for oxygen migration in Ca-doped BaGdInO4 is lower as compared to undoped BaGdInO4 and importantly divalent doping will form oxygen vacancies. The results are consistent with recent experimental work that determined an increase in the diffusivity of Ca-doped BaGdInO4 as compared to the undoped case. Additionally, the most thermodynamically feasible defect in this material is the GdIn anti-site. Promising isovalent dopants on the Ba, Gd and In were found to be the Sr, Al and Sc respectively. The most favourable dopant on the Gd site to produce oxygen vacancies is Ca and its solution energy is lower only by 0.02 eV than that calculated for Sr. Ba2+ ion conduction in this material is slow with the migration energy barrier being higher than 2 eV.

Synthesis of Borate Doped La10Ge6O27: Confirming the Presence of a Secondary Conducting Pathway

Lanthanum silicate/germanate apatite materials have attracted significant interest as Solid Oxide Fuel Cell electrolytes due to their high oxide ionic conductivity at lower temperatures (500-800 ⁰C). In these structures, oxide ion conduction is due to interstitial pathways associated with the high oxygen excess within the structures. Therefore, cation doped La8+xA2-x(M6-xBxO4)O2+x/2 (A = Ca, Sr, Ba; M = Si and Ge; B = Mg, Ga, Al, Zn, B) have been reported to increase oxide ion conductivity via the introduction of excess oxide ions.[1-3] Whilst apatite silicate has higher conductivities at lower temperatures due to lower activation energies, apatite germanates can achieve higher oxygen excess and therefore higher conductivities at elevated temperatures. However, in increasing oxygen content there is a change in symmetry from hexagonal to triclinic leading to a subsequent reduction in conductivity.[4] Previous studies have shown the issue may be overcome by the incorporation of Y doping e.g La8Y2GeO6O27 which leads to stabilisation of the higher conducting hexagonal phase.[5] Herein, we demonstrate the successful incorporation of borate into La10-xYxGeO6O27 and show that it also stabilises the higher conducting hexagonal form. We show that B can be doped into both the Ge site and the oxide ion channels. Interestingly, the conductivity of samples with borate in the channels (which would be expected to block channel oxide ion conductivity along the c direction) is still reasonably high, which supports suggestions that there is significant conduction perpendicular to the channels in these apatite germanates.[1] A Orera and P R Slater, Chem. Mater 2010 22 675-690[2] P M Panchmatia, A Orera, G J Rees, M E Smith, J. V. Hanna, P. R. Slater and M. S. Islam, Angew. Chem. Int. Ed, 2011 50 9328-9333[3] E Kendrick, M S Islam and P R Slater, J. Mater. Chem 2007 17 3104-3111.[4] M S Chambers, P Chater, I R Evans and J S Evans, Inorg. Chem., 2019 58(21)14853-14862,[5] A Najib, J. E. H. Sansom, J. R. Tolchard, P. R. Slater and M. S. Islam, Dalton Trans., vol. 19, pp. 3106-3109, 2004.

Oxygen ion conductivity studies of bismuth and bismuth-calcium co-doped ThO2

A series of trivalent (Bi3+) doped and divalent (Ca2+) co-doped ThO2 samples i.e., Th0.50-xCaxBi0.50O2-δ (x = 0.00, 0.05, 0.10, 0.15 and 0.20) have been synthesized by citrate-nitrate solution combustion route and investigated in the context of oxygen ion conductivity and dielectric relaxation phenomena. The Rietveld refinement of the Powder X-ray diffraction data confirmed monophasic fluorite structures (S.G. Fm3‾m) for calcium concentrations up to 20 mol %. The optical band gap decreased with the increase in Ca2+ concentration up to 10 mol %. In contrast, the defect band's intensity in the Raman spectra increased due to oxygen vacancies on divalent addition. The quantitative aspect of oxygen vacancy and defect concentration was derived from Raman spectra. The crystallographic index application was further employed to interpret the optimum doping concentration to maximize oxide ion conductivity. Remarkably high oxide ion conductivity (~10−3 S/cm) was observed for Bi3+ doped (50 mol %), and Bi3+ (50 mol %)-Ca2+ (10 mol %) co-doped ThO2 samples at 773 K. The Nyquist plot exhibited grain contribution for low dopant levels. Both grain and grain boundary contribution were present in the higher dopant concentrations. Conductivity, dielectric, and modulus properties of doped and co-doped samples have been compared, from which 10 mol % of Ca2+-doping was identified to be the optimum concentration.

Production of crystal-oriented lanthanum silicate oxyapatite ceramics with anisotropic electrical conductivity and thermal expansion

Lanthanum silicate oxyapatite (LSO) has a very high oxide-ion conductivity along the c-axis of its hexagonal crystal. The effect of the crystal orientation in LSO ceramics on the anisotropy of their electrical and mechanical properties has not been studied systematically because centimeter-scale ceramics with different degrees of crystal orientation are difficult to produce. We produced crystal-oriented LSO ceramics by slip casting under a strong magnetic field and subsequent sintering. Using LSO ceramics with different degrees of crystal orientation, the electrical conductivity (σ) and linear thermal expansion coefficient (α) were measured. σ parallel to the c-axis (σ||c) increased as the degree of crystal orientation increased, whereas σ perpendicular to the c-axis (σ⊥c) was relatively insensitive to this parameter. The σ||c and σ⊥c values of our samples were almost the same as those of LSO single crystals. α also exhibited anisotropy originating from the asymmetry of the crystal structure.