ABSTRACT
Proton conductors have potential applications such as fuel cells, electrolysis cells, and sensors. These applications require new materials with high proton conductivity and high chemical stability at intermediate temperatures. Herein we report a series of new hexagonal perovskite-related oxides, Ba5R2Al2SnO13 (R = Gd, Dy, Ho, Y, Er, Tm, and Yb). Ba5Er2Al2SnO13 exhibited a high proton conductivity without chemical doping (e.g., 0.01 S cm-1 at 303 °C), which is attributed to its high proton concentration and diffusion coefficient. The high diffusion coefficient of Ba5Er2Al2SnO13 can be attributed to the fast proton migration in the octahedral layers. The high proton concentration is attributed to full hydration in hydrated Ba5Er2Al2SnO13 and the large amount of intrinsic oxygen vacancies in the dry sample, as evidenced by both neutron diffraction and thermogravimetric analysis. Ba5Er2Al2SnO13 was found to exhibit high chemical stability under wet atmospheres of O2, air, H2, and CO2. High proton conductivity and high chemical stability indicate that Ba5Er2Al2SnO13 is a superior proton conductor. Ba5R2Al2SnO13 (R = Gd, Dy, Ho, Y, Tm, and Yb) exhibited high electrical conductivity in wet N2, suggesting that these materials also exhibit high proton conductivity. These findings will open new avenues for proton conductors. The high proton conductivity via full hydration and fast proton migration in octahedral layers in highly oxygen-deficient hexagonal perovskite-related materials would be an effective strategy for developing next-generation proton conductors.
ABSTRACT
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.
ABSTRACT
A new sodium tellurate has been hydrothermally synthesized and comprehensively analysed using spectroscopic and thermogravimetric techniques, resulting in the determination of its composition as NaTeO3(OH). The analysis of synchrotron X-ray and neutron diffraction data indicates that NaTeO3(OH) has a crystal structure similar to that of the previously reported tellurate, KTeO3(OH), with the space group P21/a (No. 14). NaTeO3(OH) consists of zigzag one-dimensional chains built by edge-sharing TeO6 octahedra, running parallel to the c-axis and connected to sodium and hydrogen atoms. The hydrogen atoms covalently bond to the terminal oxygen atoms on the one-dimensional chain and also form hydrogen bonds with other terminal oxygen atoms on nearby chains. The structure has been confirmed by optimization using the pseudopotential method and performing Bond Valence Sum (BVS) analysis. Although Li+ ions in LiTeO3(OH) can be exchanged reversibly with H+ ions, no ion exchange behaviour is observed in NaTeO3(OH). The difference is attributed to the size of the alkali ions and their crystal structure.
ABSTRACT
The Li3MX6 compounds (M=Sc, Y, In; X=Cl, Br) are known as promising ionic conductors due to their compatibility with typical metal oxide cathode materials. In this study, we have successfully synthesized γ-Li3ScCl6 using high pressure for the first time in this family. Structural analysis revealed that the high-pressure polymorph crystallizes in the polar and chiral space group P63mc with hexagonal close-packing (hcp) of anions, unlike the ambient-pressure α-Li3ScCl6 and its spinel analog with cubic closed packing (ccp) of anions. Investigation of the known Li3MX6 family further revealed that the cation/anion radius ratio, rM/rX, is the factor that determines which anion sublattice is formed and that in γ-Li3ScCl6, the difference in compressibility between Sc and Cl exceeds the ccp rM/rX threshold under pressure, enabling the ccp-to-hcp conversion. Electrochemical tests of γ-Li3ScCl6 demonstrate improved electrochemical reduction stability. These findings open up new avenues and design principles for lithium solid electrolytes, enabling routes for materials exploration and tuning electrochemical stability without compositional changes or the use of coatings.
ABSTRACT
Ion conductors comprising noncentrosymmetric frameworks have emerged as new functional materials. However, strongly correlated polarity functionality and ion transport have not been achieved. Herein, we report a ferroelectric proton conductor, K2MnN(CN)4·H2O (1·H2O), exhibiting the strong correlation between its polar skeleton and conductive ions that generate anomalous ferroelectricity via the proton-bias phenomenon. The application of an electric field of ±1 kV/cm (0.1 Hz) on 1·H2O at 298 K produced the ferroelectricity (polarization = 1.5 × 104 µC/cm2), which was enhanced by the ferroelectric-skeleton-trapped conductive protons. Furthermore, the strong polarity-proton transport coupling of 1·H2O induced a proton-rectification-like directional ion-conductive behavior that could be adjusted by the magnitude and direction of DC electric fields. Moreover, 1·H2O exhibited reversible polarity switching between the polar 1·H2O and its dehydrated form, 1, with a centrosymmetric structure comprising an order-disorder-type transition of the nitrido-bridged chains.
ABSTRACT
Proton conductors are attractive materials with a wide range of potential applications such as proton-conducting fuel cells (PCFCs). The conventional strategy to enhance the proton conductivity is acceptor doping into oxides without oxygen vacancies. However, the acceptor doping results in proton trapping near dopants, leading to the high apparent activation energy and low proton conductivity at intermediate and low temperatures. The hypothetical cubic perovskite BaScO2.5 may have intrinsic oxygen vacancies without the acceptor doping. Herein, we report that the cubic perovskite-type BaSc0.8Mo0.2O2.8 stabilized by Mo donor-doing into BaScO2.5 exhibits high proton conductivity within the 'Norby gap' (e.g., 0.01 S cm-1 at 320 °C) and high chemical stability under oxidizing, reducing and CO2 atmospheres. The high proton conductivity of BaSc0.8Mo0.2O2.8 at intermediate and low temperatures is attributable to high proton concentration, high proton mobility due to reduced proton trapping, and three-dimensional proton diffusion in the cubic perovskite stabilized by the Mo-doping into BaScO2.5. The donor doping into the perovskite with disordered intrinsic oxygen vacancies would be a viable strategy towards high proton conductivity at intermediate and low temperatures.
ABSTRACT
α-FAPbI3 (FA+ = CH(NH2)2+) with a cubic perovskite structure is promising for photophysical applications. However, α-FAPbI3 is metastable at room temperature, and it transforms to the δ-phase at a certain period of time at room temperature. Herein, we report a thiocyanate-stabilized pseudo-cubic perovskite FAPbI3 with ordered columnar defects (α'-phase). This compound has a â5ap × â5ap × ap tetragonal unit cell (ap: cell parameter of primitive perovskite cell) with a band gap of 1.91 eV. It is stable at room temperature in a dry atmosphere. Furthermore, the presence of the α'-phase in a mixed sample with the δ-phase drastically reduces the δ-to-α transition temperature measured on heating, suggesting the reduction of the nucleation energy of the α-phase or thermodynamic stabilization of the α-phase through epitaxy. The defect-ordered pattern in the α'-phase forms a coincidence-site lattice at the twinned boundary of the single crystals, thus hinting at an epitaxy- or strain-based mechanism of α-phase formation and/or stabilization. In this study, we developed a new strategy to control defects in halide perovskites and provided new insight into the stabilization of α-FAPbI3 by pseudo-halide and grain boundary engineering.
ABSTRACT
Band gap engineering using multiple anions is an established approach to novel photocatalysts that exhibit suitable band gap energies for water splitting and high photocorrosion resistance. However, few studies have been conducted on photocatalysts with polyanions, including polychalcogenide ions. Here, we present a new quaternary gallium oxysulfide with disulfide pairs (S2)2-, La4Ga2S8O3, grown out of a KI molten salt. Single-crystal X-ray diffraction analysis revealed that the oxysulfide crystallizes in the orthorhombic space group Pbcn with lattice constants of a = 18.3330(6) Å, b = 13.0590(5) Å, and c = 5.9022(3) Å. In the crystal structure, the GaS4-based zigzag chains and OLa4-based fluorite-like strips are independently arranged in two dimensions, which alternately stack via the disulfide pairs along the third direction. The oxysulfide is a direct-type semiconductor with a band gap of 2.45 eV. First-principles calculations combined with X-ray photoemission spectroscopy measurements show that S 3p states derived from the disulfide pairs dominate the valence band maximum and conduction band minimum, and these band-edge positions are suitable for the oxidation and reduction of water. Our comprehensive study based on the electronic structure suggests that the disulfide pairs make La4Ga2S8O3 a potential photocatalyst for water splitting under visible-light irradiation.
ABSTRACT
The chemical order and disorder of solids have a decisive influence on the material properties. There are numerous materials exhibiting chemical order/disorder of atoms with similar X-ray atomic scattering factors and similar neutron scattering lengths. It is difficult to investigate such order/disorder hidden in the data obtained from conventional diffraction methods. Herein, we quantitatively determined the Mo/Nb order in the high ion conductor Ba7Nb4MoO20 by a technique combining resonant X-ray diffraction, solid-state nuclear magnetic resonance (NMR) and first-principle calculations. NMR provided direct evidence that Mo atoms occupy only the M2 site near the intrinsically oxygen-deficient ion-conducting layer. Resonant X-ray diffraction determined the occupancy factors of Mo atoms at the M2 and other sites to be 0.50 and 0.00, respectively. These findings provide a basis for the development of ion conductors. This combined technique would open a new avenue for in-depth investigation of the hidden chemical order/disorder in materials.
ABSTRACT
Redox photosensitisers (PSs) play essential roles in various photocatalytic reactions. Herein, we synthesised new redox PSs of 1 : 1 supramolecules that comprise a ring-shaped Re(i) tetranuclear complex with 4+ charges and a Keggin-type heteropolyoxometalate with 4- charges. These PSs photochemically accumulate multi-electrons in one molecule (three or four electrons) in the presence of an electron donor and can supply electrons with different reduction potentials. PSs were successfully applied in the photocatalytic reduction of CO2 using catalysts (Ru(ii) and Re(i) complexes) and triethanolamine as a reductant. In photocatalytic reactions, these supramolecular PSs supply a different number of electrons to the catalyst depending on the redox potential of the intermediate, which is made from the one-electron-reduced species of the catalyst and CO2. Based on these data, information on the reduction potentials of the intermediates was obtained.
ABSTRACT
Oxide-ion conductors, also known as "oxygen ion conductors," have garnered significant attention in recent years due to their extensive applications in a variety of electrochemical devices, including oxygen concentrators, solid-oxide fuel cells (SOFCs), and solid oxide electrolysis cells. The key to improving the performance of these devices is the creation of novel oxide-ion conductors. In this feature article, we discuss the recent developments of new structural families of oxide-ion conductors and of the Dion-Jacobson-type layered oxide-ion conductors with a particular emphasis on CsM2Ti2NbO10-δ (M = Bi and lanthanoids; δ represents oxygen-vacancy content) and their solid solutions. CsBi2Ti2NbO10-δ is the first example of an oxide-ion conductor with a Dion-Jacobson-type layered perovskite structure, and the structural characteristics of these materials are extracted here. We have proposed an original concept that the large sized Cs+ cations and M3+ displacements yield the large bottlenecks for oxide-ion migration, which would facilitate the discovery of novel oxide-ion conductors. This article presents evidence that Dion-Jacobson-type layered perovskites are superior oxide-ion conductors. We also demonstrate how the information gleaned from these studies can be applied to the design of novel oxide-ion conductors.
ABSTRACT
Transition-metal oxynitrides have a variety of functions such as visible light-responsive catalysts and dielectric materials, but acquiring single crystals necessary to understand inherent properties is difficult and is limited to relatively small sizes (<10 µm) because they easily decompose at high temperatures. Here, we have succeeded in growing platelet single crystals of TaON with a typical size of 50 × 100 × 10 µm3 under a high pressure and high temperature (6 GPa and 1400 °C) using a LiCl flux. Such a harsh condition, in contrast to powder samples synthesized under mild conditions, resulted in the introduction of a large amount of oxygen vacancies (x = 0.06 in TaO1-xN) into the crystal, providing a metallic behavior with a large anisotropy of ρc/ρab â¼ 103. Low-temperature oxygen annealing allows for a single-crystal-to-single-crystal transformation to obtain fully oxidized TaON (yellow) crystals. Needle-like crystals can be obtained when NH4Cl is used as a flux. Furthermore, black Hf2ON2 single crystals are also grown, suggesting that the high-pressure flux method is widely applicable to other transition-metal oxynitrides, with extensive carrier control.
ABSTRACT
In the present work, we have discovered the first example of a CaEu2Ge3O10-type oxide-ion conductor, Ca1.05Sm1.95Ge3O9.975. The CaEu2Ge3O10-type structure was selected by screening 624 Ge-containing materials by the bond-valence-based-energy calculations. CaEu2Ge3O10-type CaEu2Ge3O10, CaGd2Ge3O10, and a new material CaSm2Ge3O10 were synthesized. CaSm2Ge3O10 showed the highest electrical conductivity among these three materials. Ca1+xSm2-xGe3O10-x/2 (x = 0.05, 0.1, and 0.2) were also synthesized, and we found that Ca1.05Sm1.95Ge3O9.975 exhibited the highest conductivity of 1.2 × 10-5 S cm-1 at 1373 K. Oxygen transport numbers in Ca1.05Sm1.95Ge3O9.975 were determined to be 0.64(5) at 1073 K and 0.65(8) at 1123 K, which indicates that the major carrier is the oxide ion. Therefore, CaEu2Ge3O10-type Ca1.05Sm1.95Ge3O9.975 is a new structure family of oxide-ion conductors. The crystal structures of the new materials CaSm2Ge3O10 and Ca1.05Sm1.95Ge3O9.975 were successfully analyzed by the CaEu2Ge3O10-type structure (space group P21/c) using the single-crystal X-ray diffraction data. The bond-valence-based-energy calculation for the refined crystal structure of Ca1.05Sm1.95Ge3O9.975 suggested that oxide ions migrate along the [2 0 1], [0 1 0], and [12.88 6.43 1] directions with energy barriers of 0.88, 0.92, and 1.1 eV, respectively, which indicates three-dimensional oxide-ion diffusion in Ca1.05Sm1.95Ge3O9.975.
ABSTRACT
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.
ABSTRACT
Narrow-gap semiconductors with visible light absorption capability have attracted attention as photofunctional materials. H--doped BaSn0.7Y0.3O3-δ containing Sn(II) species was recently reported to absorb visible light up to 600 nm, which represents the first demonstration of oxyhydride-based visible-light-absorbers. In the present study, a more detailed investigation was made to obtain information on the synthesis and properties of H--doped perovskite-type stannate with respect to the A-site cation of the material and the preparation conditions. H--doped ASn0.7Y0.3O3-δ (A = Ba, Ba0.5Sr0.5, and Sr) obtained by the reaction of ASn0.7Y0.3O3-δ precursors with CaH2 at 773 K under vacuum conditions was shown to have almost the same bandgap (ca. 2.1 eV), regardless of the A-site cation. Physicochemical measurements and theoretical calculations revealed that the identical bandgaps of H--doped ASn0.7Y0.3O3-δ are due to the simultaneous shift of the midgap states composed of Sn2+ with the conduction band minimum. Experimental results also indicated that the appropriate preparation conditions with respect to Y3+-substitution and the temperature for the synthesis of the ASn0.7Y0.3O3-δ precursors were essential to obtain H--doped products that have a low density of defects.
ABSTRACT
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.
ABSTRACT
Honeycomb layered oxides constitute an emerging class of materials that show interesting physicochemical and electrochemical properties. However, the development of these materials is still limited. Here, we report the combined use of alkali atoms (Na and K) to produce a mixed-alkali honeycomb layered oxide material, namely, NaKNi2TeO6. Via transmission electron microscopy measurements, we reveal the local atomic structural disorders characterised by aperiodic stacking and incoherency in the alternating arrangement of Na and K atoms. We also investigate the possibility of mixed electrochemical transport and storage of Na+ and K+ ions in NaKNi2TeO6. In particular, we report an average discharge cell voltage of about 4 V and a specific capacity of around 80 mAh g-1 at low specific currents (i.e., < 10 mA g-1) when a NaKNi2TeO6-based positive electrode is combined with a room-temperature NaK liquid alloy negative electrode using an ionic liquid-based electrolyte solution. These results represent a step towards the use of tailored cathode active materials for "dendrite-free" electrochemical energy storage systems exploiting room-temperature liquid alkali metal alloy materials.
ABSTRACT
We report on the growth of single crystals of an electron-doped titanium oxyfluoride, Li2Ti(O,F)3, employing high-temperature electrolysis of TiO2 with a eutectic Li2MoO4-LiF melt. Greenish octahedral-shaped crystals (â¼30 µm in size) with a cubic rocksalt-type structure were successfully obtained by precisely tuning the applied voltage. The temperature-dependent magnetic susceptibility data revealed a paramagnetic behavior at low temperatures, ensuring the presence of Ti3+ ions (mean valence number of +3.78; F/Ti â¼ 0.15). The crystals exhibited clear visible-light absorption and produced H2 from water in the presence of a sacrificial reagent under UV-light irradiation. Li2Ti(O,F)3 more efficiently produced H2 compared with a nondoped oxyfluoride Li5Ti2O6F, likely due to the doped electrons for the former. This work highlights a promising electrochemical approach toward growing electron-doped oxyfluoride crystals.
ABSTRACT
The main approach for exploring metastable materials is via trial-and-error synthesis, and there is limited understanding of how metastable materials are kinetically stabilized. In this study, a metastable phase superionic conductor, ß-Li3 YCl6 , is discovered through in situ X-ray diffraction after heating a mixture of LiCl and YCl3 powders. While Cl- arrangement is represented as a hexagonal close packed structure in both metastable ß-Li3 YCl6 synthesized below 600 K and stable α-Li3 YCl6 above 600 K, the arrangement of Li+ and Y3+ in ß-Li3 YCl6 determined by neutron diffraction brought about the cell with a 1/â3 a-axis and a similar c-axis of stable α-Li3 YCl6 . Higher Li+ ion conductivity and lower activation energy for Li+ transport are observed in comparison with α-Li3 YCl6 . The computationally calculated low migration barrier of Li+ supports the low activation energy for Li+ conduction, and the calculated high migration barrier of Y3+ kinetically stabilizes this metastable phase by impeding phase transformation to α-Li3 YCl6 . This work shows that the combination of in situ observation of solid-state reactions and computation of the migration energy can facilitate the comprehension of the solid-state reactions allowing kinetic stabilization of metastable materials, and can enable the discovery of new metastable materials in a short time.