Comprehensive understanding of the crystal structure of perovskite-type Ba3Y4O9 with Zr substitution: a theoretical and experimental study.

We previously reported that Zr substitution improves the chemical stability of Ba3Y4O9 and nominally 20 mol% Zr-substituted Ba3Y4O9 is an oxide-ion conductor at intermediate temperatures (500-700 °C). However, the influence of Zr substitution on the structural properties of Ba3Y4O9 was poorly understood. This paper aims to comprehensively understand the crystal structure of Ba3Y4O9 with Zr substitution by powder X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS) measurements, and first-principles calculations. From the results, firstly we found that the hexagonal unit cell of Ba3Y4O9 reported in the database should be revised as doubled along the c-axis in terms of the periodicity of oxide-ion positions. The revised unit cell of Ba3Y4O9 consists of 18 layers of BaO3 and 24 layers of Y which periodically stack along the c-axis. In this work, we focused on the cationic lattice and noticed that the periodical stacking of Ba and Y layers comprises a similar sequence to that in the body-centered cubic (BCC) structure. There are two regions in the Ba3Y4O9 structure: one is a hetero-stacking region of Ba and Y layers (Ba-Y-Ba-Y-Ba) and the other is a homo-stacking region (Ba-Y-Y-Ba). It is noteworthy that the former region is similar to a cubic perovskite. In Zr-substituted Ba3Y4O9, Zr ions preferentially substitute for Y ions in the hetero-stacking region, and therefore the local environment of Zr ions in Ba3Y4O9 is quite similar to that in BaZrO3. Besides, the Zr substitution for Y in Ba3Y4O9 increases the fraction of the cubic-perovskite-like region in the stacking sequences. The structural change in the long-range order strongly affects the other material properties such as chemical stability and the ionic-conduction mechanism. Our adopted description of perovskite-related compounds based on the stacking sequence of the BCC structure should help in understanding the complex structure and developing new perovskite-related materials.

Theoretical and Experimental Studies on the Ability of Intracrystalline Pores of ß-La2(SO4)3 To Accommodate Various Gas Species with a Special Focus on Ammonia Insertion Behaviors.

ß-La2(SO4)3 is a microporous inorganic crystal with one-dimensional perforated pores where H2O molecules can be inserted. To evaluate the nature of the pores and extend the application range, we investigate the ability to accommodate various hydrogen compound molecules XHn (CH4, NH3, HF, H2S, HCl, and HI) by insertion. The stable structures of the XHn molecules in the pores of ß-La2(SO4)3 and the change in the Gibbs energy for XHn insertion ΔinsertG (T) are estimated by first-principles calculations. The guest XHn molecules are stabilized by forming H-O and X-La bonds with the ß-La2(SO4)3 host structure. Based on the values of ΔinsertG (T), NH3, H2O, and HF are energetically stable in the crystal even above 0 °C. Correspondingly, thermogravimetry (TG) of ß-La2(SO4)3 in NH3, CH4, and CO2 gases revealed that NH3 can be inserted into ß-La2(SO4)3 below 360 °C, but CH4 and CO2 cannot. Unlike the case of H2O insertion, NH3 insertion proceeds via two steps. The first step is a single-solid-phase reaction of ß-La2(SO4)3·yNH3, where NH3 molecules are inserted into the host structure with a continuously changing nonstoichiometric y value between 0 and 0.1. The second step is a two-solid-phase reaction between ß-La2(SO4)3·0.1NH3 and ß'-La2(SO4)3·0.3NH3, which is a phase formed after further NH3 insertion into ß-La2(SO4)3·0.1NH3 with a minor change in the host structure. The fact that both NH3 and H2O can be inserted confirms that the pores of ß-La2(SO4)3 allow for the insertion of molecules with a strong polarity. This nature is similar to zeolites and metal-organic frameworks (MOFs) with polar surfaces in the pores.

Theoretical study on proton diffusivity in Y-doped BaZrO3 with realistic dopant configurations.

We theoretically revisit the proton diffusivity in yttrium-doped barium zirconate (Y-doped BaZrO3) with realistic dopant configurations under processing conditions. In a recent study employing the replica exchange Monte Carlo method, the equilibrium Y configurations at typical sintering temperatures were shown to deviate from the random configuration assumed in earlier theoretical studies. In the present study, we took this observation into account and evaluated the effect of the Y configuration on the proton diffusivity. Using the master equation approach based on local diffusion barriers calculated from first principles, the proton diffusivities under realistic Y configurations were estimated to be higher than those in the random configuration. This is explained by the fact that realistic Y configurations have fewer trap sites with deep potential wells compared to the random configuration due to the isolation trend of Y dopants. In addition, the effects of proton-proton interaction and the abundance of preferential conduction pathways are discussed; it is found that both are relatively minor factors compared to the trap site effect in determining the dependence of the proton diffusivity on the Y configurations.

Proton Conductive BaZr0.8-x Cex Y0.2 O3-δ : Influence of NiO Sintering Additive on Crystal Structure, Hydration Behavior, and Conduction Properties.

Y-doped BaZrO3 , BaCeO3 and BaZr1-x Cex O3 show high proton conductivity at intermediate temperature and are promising electrolyte candidates in electrochemical devices. However, in most cases, the present cell fabrication process seems to be unavailable to avoid the addition of NiO, which is either added to improve the sinterability of these electrolyte or diffuses from the electrode substrate during co-sintering. In this work, a systematic investigation was performed to study the effect of NiO on BaZr0.8-x Cex Y0.2 O3-δ (BZCY20) covering the full Ce range from 0 to 0.8. The results revealed that regardless of the composition of BZCY20, both the dehydration temperature and proton concentration decreased by adding NiO, which further greatly decreased the ionic conductivity and the transport number. And it is found that the redox cycles in Ce-rich samples containing Ni makes the grain boundary conductivity worse and the electrolyte brittle. The conclusion is that NiO is detrimental to the performance of the electrochemical cells using these materials as the electrolyte, although compromise might be achieved in certain degree by tuning the Ce content. However, it should be noted that to further improve the cell performance, a new sintering additive or new processing for cell fabrication is essential.

Experimental Study of Hydration/Dehydration Behaviors of Metal Sulfates M2(SO4)3 (M = Sc, Yb, Y, Dy, Al, Ga, Fe, In) in Search of New Low-Temperature Thermochemical Heat Storage Materials.

To identify potential low-temperature thermochemical heat storage (TCHS) materials, hydration/dehydration reactions of M2(SO4)3 (M = Sc, Yb, Y, Dy, Al, Ga, Fe, In) are investigated by thermogravimetry (TG). These materials have the same rhombohedral crystal structure, and one of them, rhombohedral Y2(SO4)3, has been recently proposed as a promising material. All M2(SO4)3·xH2O hydrate/dehydrate reversibly between 30 and 200 °C at a relatively low p H2O (=0.02 atm). Among them, rare-earth (RE) sulfates RE2(SO4)3·xH2O (RE = Sc, Yb, Y, Dy) show narrower thermal hystereses (less than 50 °C), indicating that they have faster reaction rates than the other sulfates M2(SO4)3·xH2O (M = Al, Ga, Fe, In). As for the heat storage density, Y2(SO4)3·xH2O is most promising due to the largest mass change (>10 mass % anhydrous basis) during the reactions. This is larger than that of the existing candidate CaSO4·0.5H2O (6.6 mass % anhydrous basis). Regarding the reaction temperature of the water insertion into rhombohedral RE2(SO4)3 (RE = Yb, Y, Dy) to form RE2(SO4)3·H2O, it increases as the ionic radius of RE3+ becomes larger. Since such a relationship is also observed in ß-RE2(SO4)3·xH2O, RE(OH)3, and REPO4·xH2O, this empirical knowledge should be useful to expect the dehydration/hydration reaction temperatures of the RE compounds.

Multi-step hydration/dehydration mechanisms of rhombohedral Y2(SO4)3: a candidate material for low-temperature thermochemical heat storage.

To evaluate rhombohedral Y2(SO4)3 as a new potential material for low-temperature thermochemical energy storage, its thermal behavior, phase changes, and hydration/dehydration reaction mechanisms are investigated. Rhombohedral Y2(SO4)3 exhibits reversible hydration/dehydration below 130 °C with relatively small thermal hysteresis (less than 50 °C). The reactions proceed via two reaction steps in approximately 0.02 atm of water vapor pressure, i.e. "high-temperature reaction" at 80-130 °C and "low-temperature reaction" at 30-100 °C. The high-temperature reaction proceeds by water insertion into the rhombohedral Y2(SO4)3 host structure to form rhombohedral Y2(SO4)3·xH2O (x = ∼1). For the low-temperature reaction, rhombohedral Y2(SO4)3·xH2O accommodates additional water molecules (x > 1) and is eventually hydrated to Y2(SO4)3·8H2O (monoclinic) with changes in the host structure. At a water vapor pressure above 0.08 atm, intermediate Y2(SO4)3·3H2O appears. A phase stability diagram of the hydrates is constructed and the potential usage of Y2(SO4)3 for thermal energy upgrades is assessed. The high-temperature reaction may act similarly to an existing candidate, CaSO4·0.5H2O, in terms of reaction temperature and water vapor pressure. Additionally, the hydration of rhombohedral Y2(SO4)3·xH2O to Y2(SO4)3·3H2O should exhibit a larger heat storage capacity. With respect to the reaction kinetics, the initial dehydration of Y2(SO4)3·8H2O to rhombohedral Y2(SO4)3 introduces a microstructure with pores on the micron order, which might enhance the reaction rate.

Correlation between Concentrations of Ni and Y in Y-Doped BaZrO3 Electrolyte in Co-Sintered Cells: A Case of Controlled NiO Activity by Using MgO-NiO Solid Solution as Anode Substrate.

BaZr0.8Y0.2O3-δ (BZY20) is promising to be applied as an electrolyte in fuel cells, electrolysis cells, etc. However, when a half cell composed of a BZY20 electrolyte layer and a BZY20-NiO composite anode substrate is co-sintered (1400-1600 °C), Ni diffuses from the anode substrate into the electrolyte layer. Y content in the electrolyte layer decreases dramatically, since BZY20 cannot be equilibrated with NiO at such high temperature. Such Ni diffusion and Y loss are detrimental to the electrochemical performance of the electrolyte layer. In this work, we added MgO-NiO solid solution into the anode substrate to adjust the NiO activity (aNiO) during the co-sintering process, and used three different co-sintering methods to control the BaO activity (aBaO). The results revealed that by decreasing aNiO in the system, the as-co-sintered electrolyte layer had the composition shifting towards the direction of high Y and low Ni cation ratios. A clear correlation between the intra-grain concentration of Ni and Y was confirmed. In other words, to prepare the electrolyte with the same Y cation ratio, the Ni diffusion into the electrolyte layer can be suppressed by using the MgO-NiO solid solution with a high MgO ratio and a low Ni ratio. Moreover, by increasing aBaO, we found that the Y cation ratio increased and approached the nominal value of the pristine BZY20, when Mg1-xNixO (x = 0.3 and 0.5) was used. In summary, both aNiO and aBaO play important roles in governing the composition of the electrolyte layer prepared by the co-sintering process. To evaluate the quality of the electrolyte layer, both the intra-grain Y and Ni concentrations should be carefully checked.

Correlation between Phase Behavior and Electrical Conductivity of 10 mol % Y-Doped BaZrO3: An Anomalous Dispersion Effect-Aided Synchrotron Radiation XRD Study Combined with TEM Observation and Electrochemical Analysis.

Y-doped BaZrO3 (BZY) has high proton conductivity and is a promising electrolyte candidate for fuel cells and electrolytic cells at an intermediate temperature range. However, the conductivity of BZY has a large discrepancy in the literature. In particular, for BaZr0.9Y0.1O3-δ (BZY10), the reported bulk conductivity varies in the range of more than 2 orders of magnitude. With the aim of revealing the reason, in this work, we conducted synchrotron radiation X-ray diffraction analysis on a BZY10. The X-ray was adjusted to 17.027 keV to approach the Y-K absorption edge (17.037 keV), and the anomalous dispersion effect was thereby activated for a precise distinction between Zr and Y. High-resolution scanning transmission electron microscopy observation and electrochemical measurements were also performed. Assisted by these experimental results, Rietveld refinement with greatly improved quality was thereby available to generate precise information on both the phase behavior and crystal structure. The results revealed that the BZY10 samples after sintering at 1600 °C for 8 to 200 h have a bimodal microstructure. They were not single phases, but mixtures of two perovskite phases differing slightly in Y contents. The Y contents in the two phases after sintering for 8 h were about 12.3 and 8.7 mol %, respectively, and finally became 10.6 and 9.2 mol %, respectively, after sintering for 200 h. In addition, the partition of Y over both the Ba and Zr sites was not suggested, although small Ba-deficiency around 0.05 formed in the sample sintered for 40 h or longer. But notably, the formation of the Ba vacancies is reasonably believed as the possible reason for the decrease in bulk and also grain boundary conductivities.

Detrimental Effect of Sintering Additives on Conducting Ceramics: Yttrium-Doped Barium Zirconate.

Y-doped BaZrO3 (BZY) is currently the most promising proton-conductive ceramic-type electrolyte for application in electrochemical devices, including fuel cells and electrolyzer cells. However, owing to its refractory nature, sintering additives, such as NiO, CuO, or ZnO are commonly added to reduce its high sintering temperature from 1600 °C to approximately 1400 °C. Even without deliberately adding a sintering additive, the NiO anode substrate provides another source of the sintering additive; during the co-sintering process, NiO diffuses from the anode into the BZY electrolyte layer. In this work, a systematic study of the effect of NiO, CuO, and ZnO on the electroconductive properties of BaZr0.8 Y0.2 O3-δ (BZY20) is conducted. The results revealed that the addition of NiO, CuO, or ZnO into BZY20 not only degraded the electrical conductivity but also resulted in enhancement of the hole conduction. Removal of these sintering additives can be realized by post-annealing in hydrogen at a mild temperature of 700 °C, but it is kinetically very slow. Therefore, the addition of NiO, CuO, and ZnO is detrimental to the electroconductive properties of BZY20, and significantly restrict its application as an electrolyte. The development of new sintering additives, new anode catalysts, or new methods for preparing BZY electrolyte-based cells is urgently needed.

La2(Nb1-xYx)2O7-δ: discovery of a novel fluorite structure-based ionic conductor.

A novel fluorite structure-based compound of La2(Nb1-xYx)2O7-δ shows superior chemical stability and proton conduction.

Discovery of Rapid and Reversible Water Insertion in Rare Earth Sulfates: A New Process for Thermochemical Heat Storage.

Thermal energy storage based on chemical reactions is a prospective technology for the reduction of fossil-fuel consumption by storing and using waste heat. For widespread application, a critical challenge is to identify appropriate reversible reactions that occur below 250 °C, where abundant low-grade waste heat and solar energy might be available. Here, it is shown that lanthanum sulfate monohydrate La2 (SO4 )3 ⋅H2 O undergoes rapid and reversible dehydration/hydration reactions in the temperature range from 50 to 250 °C upon heating/cooling with remarkably small thermal hysteresis (<50 °C), and thus it emerges as a new candidate system for thermal energy storage. Thermogravimetry and X-ray diffraction analyses reveal that the reactions proceed through an unusual mechanism for sulfates: water is removed from, or inserted in La2 (SO4 )3 ⋅H2 O with progressive change in hydration number x without phase change. It is also revealed that only a specific structural modification of La2 (SO4 )3 exhibits this reversible dehydration/hydration behavior.

Tetravalent dysprosium in a perovskite-type oxide.

The existence of tetravalent dysprosium in perovskite-type oxide barium zirconate is confirmed in this work. This discovery will stimulate many researchers in diverse fields such as catalysts, solid state ionics, sensors, and fluorescent materials.

Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes.

The compound CsH2PO4 has emerged as a viable electrolyte for intermediate temperature (200-300 degrees C) fuel cells. In order to settle the question of the high temperature behavior of this material, conductivity measurements were performed by two-point AC impedance spectroscopy under humidified conditions (p[H2O] = 0.4 atm). A transition to a stable, high conductivity phase was observed at 230 degrees C, with the conductivity rising to a value of 2.2 x 10(-2) S cm(-1) at 240 degrees C and the activation energy of proton transport dropping to 0.42 eV. In the absence of active humidification, dehydration of CsH2PO4 does indeed occur, but, in contradiction to some suggestions in the literature, the dehydration process is not responsible for the high conductivity at this temperature. Electrochemical characterization by galvanostatic current interrupt (GCI) methods and three-point AC impedance spectroscopy (under uniform, humidified gases) of CsH2PO4 based fuel cells, in which a composite mixture of the electrolyte, Pt supported on carbon, Pt black and carbon black served as the electrodes, showed that the overpotential for hydrogen electrooxidation was virtually immeasurable. The overpotential for oxygen electroreduction, however, was found to be on the order of 100 mV at 100 mA cm(-2). Thus, for fuel cells in which the supported electrolyte membrane was only 25 microm in thickness and in which a peak power density of 415 mW cm(-2) was achieved, the majority of the overpotential was found to be due to the slow rate of oxygen electrocatalysis. While the much faster kinetics at the anode over those at the cathode are not surprising, the result indicates that enhancing power output beyond the present levels will require improving cathode properties rather than further lowering the electrolyte thickness. In addition to the characterization of the transport and electrochemical properties of CsH2PO4, a discussion of the entropy of the superprotonic transition and the implications for proton transport is presented.

High-performance solid Acid fuel cells through humidity stabilization.

Although they hold the promise of clean energy, state-of-the-art fuel cells based on polymer electrolyte membrane fuel cells are inoperable above 100 degrees C, require cumbersome humidification systems, and suffer from fuel permeation. These difficulties all arise from the hydrated nature of the electrolyte. In contrast, "solid acids" exhibit anhydrous proton transport and high-temperature stability. We demonstrate continuous, stable power generation for both H2/O2 and direct methanol fuel cells operated at approximately 250 degrees C using a humidity-stabilized solid acid CsH2PO4 electrolyte.