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Phase segregation in hydride-forming alloys may persist under the action of multiple hydrogenation/dehydrogenation cycles. We use this effect to destabilize metal hydrides in the immiscible Mg-Mn system. Here, in the MgxMn1-x thin films, the Mg and Mn domains are chemically segregated at the nanoscale. In Mn-rich compositions, the desorption pressure of hydrogen from MgH2 is elevated at a given temperature, indicating a thermodynamic destabilization. The increase in the desorption pressure of hydrogen reaches â¼2.5 orders in magnitude for x = 0.30 at moderate temperatures. Such large thermodynamic destabilization allows the MgH2 to reversibly absorb and desorb hydrogen even at room temperature. Our strategy to use immiscible elements for destabilization of MgH2 is effective and opens up the possibility for the development of advanced and low-cost hydrogen storage and supply systems.
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The stability of a zirconium (Zr)-substituted face-centered cubic (FCC) yttrium (Y) hydride (Y1-xZrx hydride) phase was investigated experimentally and theoretically. Two possible sites for hydrogen atoms exist in the FCC structure, namely, T- and O-sites, where hydrogen is present at the center of the tetrahedron and the octahedron composed of Y and/or Zr metals. The P-C isotherms revealed that the hydrogen content per metal (H/M) with 33% Zr-substituted YH3-δ was 2.2-2.3, which was lower than the expected value calculated from the starting composition of YH3-33% ZrH2 (Y0.67Zr0.33H2.67, H/M = 2.67). Hydrogen at the O-site in Y1-xZrx hydride mainly reacted during hydrogen desorption/absorption. On the basis of theoretical analyses, the hydrogen atoms do not occupy the center of the octahedron, when at least two of the six vertices of the octahedron were composed of Zr. The O-sites, where more than two Zr atoms coordinate, nonlinearly increased with the Zr content, and when the Zr content was >50%, almost no hydrogen atoms occupy the O-sites. The theoretical discussion supported the experimental results, and the Zr substitution was confirmed to reduce the occupancy of H at the O-site in the FCC YH3 significantly.
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Nanosizing is known to affect the hydrogenation properties of magnesium. For this reason, the long period stacking ordered (LPSO) structures, made of the stacking of nanolayers of magnesium and nanolayers of Mg-A-B (with A = rare earth and B = transition metal), were herein considered. A Mg83.3Cu7.2Y9.5 LPSO compound with 18R structure was successfully synthesized. Its hydrogenation properties were investigated at temperatures between 150 and 400 °C. The X-ray diffraction (XRD) analysis indicates that the LPSO structure decomposes into magnesium hydride, yttrium hydride, and an intermetallic compound (Mg2Cu or MgCu2). The pressure composition (PC) isotherm for Mg83.3Cu7.2Y9.5 at 400 °C combined with XRD analysis allows one to understand the three-step hydrogenation pathway, detailed in this paper. At this hydrogenation temperature, the fully hydrogenated compound contains magnesium hydride exclusively crystallized in the most stable tetragonal structure (100% of α-MgH2 was formed). When the pristine LPSO was hydrogenated at lower temperature, the amount of α-MgH2 decreased, while its polymorphic structure, γ-MgH2, appeared. Finally, hydrogenation of Mg83.3Cu7.2Y9.5 at 150 °C led to the formation of γ-MgH2 with a high phase fraction (82% of γ-MgH2/MgH2). These results suggest that the crystallographic structure of the magnesium hydride can be controlled by the hydrogenation temperature of LPSO compounds.
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Thin films often exhibit fascinating properties, but the understanding of the underlying mechanism behind such properties is not simple. This is partially because of the limited structural information available. The hurdle in obtaining such information is especially high for textured thin films such as Mg-rich MgxTi1-x, a promising switchable smart coating material. Although these metastable thin films are seen as solid solution alloys by conventional crystallographic methods, their hydrogen-induced optical transition is hardly understood by a solid solution model. In this study, we collect atomic pair distribution function (PDF) data for a Mg0.7Ti0.3Hy thin film in situ on hydrogenation and successfully resolve TiH2 clusters of an average size of 30 Å embedded in the Mg matrix. This supports the chemically segregated model previously proposed for this system. We also observe the emergence of a previously unknown intermediate face-centered tetragonal phase during hydrogenation of the Mg matrix. This phase appears between Mg and MgH2 to reduce lattice mismatch, thereby preventing pulverization and facilitating rapid hydrogen uptake. This work may shed new light on the hydrogen-induced properties of Mg-rich MgxTi1-x thin films.
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Magnesium-based transition-metal hydrides are attractive hydrogen energy materials because of their relatively high gravimetric and volumetric hydrogen storage capacities combined with low material costs. However, most of them are too stable to release the hydrogen under moderate conditions. Here we synthesize the hydride of Mg2FexSi1-x, which consists of Mg2FeH6 and Mg2Si with the same cubic structure. For silicon-rich hydrides (x < 0.5), mostly the Mg2Si phase is observed by X-ray diffraction, and Mössbauer spectroscopy indicates the formation of an octahedral FeH6 unit. Transmission electron microscopy measurements indicate that Mg2FeH6 domains are nanometer-sized and embedded in a Mg2Si matrix. This synthesized metallographic structure leads to distortion of the Mg2FeH6 lattice, resulting in thermal destabilization. Our results indicate that nanometer-sized magnesium-based transition-metal hydrides can be formed into a matrix-forced organization induced by the hydrogenation of nonequilibrium Mg-Fe-Si composites. In this way, the thermodynamics of hydrogen absorption and desorption can be tuned, which allows for the development of lightweight and inexpensive hydrogen storage materials.
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Hydrogen storage is a key technology for the advancement of hydrogen and fuel cell power technologies in stationary and portable applications. MgH2, an example of a high-capacity hydrogen storage material, has two major material challenges for practical applications: slow hydrogen desorption kinetics and high hydrogen desorption temperature. Numerous studies have reported enhancements in kinetics but only a few in thermodynamics. Here, we present a simple but effective way to improve upon both the kinetic and thermodynamic aspects of desorption by utilizing the immiscibility of Mn, a non-hydrogen absorbing metal, with Mg. Mg0.25Mn0.75, prepared through ball milling MgH2 and Mn powders, is a nanocomposite where the nanometer-sized MgH2 domains are randomly embedded in a Mn matrix. This sample readily and reversibly absorbs and desorbs deuterium even at a temperature of 200 °C without the addition of any catalysts. This is nearly 180 °C lower than the typical operating temperature of conventional bulk Mg. Furthermore, at a given temperature, its deuterium desorption pressure is clearly elevated compared to that of pure Mg, indicating the destabilization of MgD2. The average crystallite size of MgD2 in deuterated Mg0.25Mn0.75 determined from X-ray diffraction data is around 9 nm. Nuclear magnetic resonance spectroscopy studies show that MgD2 domains are heavily strained and some of the D atoms are coordinated by a few Mn atoms, suggesting that a large number of lattice defects, including the partial substitution of Mg with Mn, are introduced during ball milling. Furthermore, the Mn matrix firmly locks nanosized MgD2, preventing the agglomeration of MgD2 below 250 °C. Our study suggests that a synergistic effect created by nanosizing, large lattice distortions, and robust interfaces between MgD2 and the Mn matrix can effectively and concurrently improve the kinetics and thermodynamics of MgD2 in Mg0.25Mn0.75. Our work demonstrates the possibility of utilizing the immiscibility of metals with Mg to synthesize a robust nanostructure that can alter the kinetics and stability of MgH2.
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A face-centered-cubic (FCC) YH3 phase is known to be stable only under high pressure (HP) of more than gigapascal order, and it reverts to the hexagonal YH3 ambient-pressure phase when the pressure is released. We previously found that the FCC YH3 can be stabilized even at ambient pressure by substituting Y for 10 mol % Li (LiH-stabilized YH3, LSY). The LSY was synthesized by heat treatment under gigapascal HP, but this process is unfavorable for mass production; that is, only a few tens of milligrams of a sample can be obtained in a single batch. In this study, we overcame this problem by applying a ball milling (BM) process for synthesizing the LSY phase, and the yield by the BM process reached on the order of grams. We confirmed that the structure of the BM sample was the same as that of the HP sample by X-ray diffractometry, Raman spectroscopy, and neutron total scattering pair distribution function analyses. The crystallinity of the BM sample, however, was lower than that of the HP sample. The difference in the crystallinity affects the thermal stability of the LSY. The BM sample with a lower crystallinity released hydrogen at a lower temperature. The BM sample was found to reversibly desorb/absorb hydrogen maintaining its initial FCC structure when the rehydrogenation temperature was at 423 K. However, when the rehydrogenation temperature of BM sample was more than 573 K, the FCC structure changed to the hexagonal ambient pressure phase due to thermal instability of FCC phase for the BM sample.
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Hydrogenation of nonequilibrium alloys may form nanometer-sized metal hydride clusters, depending on the alloy compositions and hydrogenation conditions. Here in the Ti-rich compositions of the immiscible Mg-Ti system MgH2 clusters are embedded in a Ti-H matrix. Our previous works have indicated that the interface energy between the two metal hydrides reduces the stability of MgH2. The aim of our study is to obtain the structural information on the nanometer-sized clusters. Indeed, MgD2 clusters embedded in a face-centered-cubic (FCC) Ti-D matrix is found in Mg0.25Ti0.75D1.65 by means of 2H magic angle spinning nuclear magnetic resonance (MAS NMR). The atomic pair distribution function (PDF) analysis of neutron total scattering data suggests that the MgD2 clusters have an orthorhombic structure, which is different from a rutile-type body-centered-tetragonal (BCT) structure of α-MgD2 observed in the Mg-rich compositions. Our results suggest that we can tune the thermodynamics of hydrogen absorption and desorption in Mg-H using the interface energy effect and accompanying stress-induced structural change, which contributes to the substantial development of lightweight and inexpensive hydrogen storage materials.
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A metal to insulator transition in integer or half integer charge systems can be regarded as crystallization of charges. The insulating state tends to have a glassy nature when randomness or geometrical frustration exists. We report that the charge glass state is realized in a perovskite compound PbCrO3, which has been known for almost 50 years, without any obvious inhomogeneity or triangular arrangement in the charge system. PbCrO3 has a valence state of Pb(2+)(0.5)Pb(4+)(0.5)Cr(3+)O3 with Pb(2+)-Pb(4+) correlation length of three lattice-spacings at ambient condition. A pressure induced melting of charge glass and simultaneous Pb-Cr charge transfer causes an insulator to metal transition and â¼10% volume collapse.
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Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups (1) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal-isotropic phase-crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be -0.84. Heating enhances the thermal cis-to-trans isomerization and subsequent cooling returned crystals of the trans/trans isomer.
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Structural changes of La2Ni7H(x) during the first and second absorption-desorption processes along the P-C isotherm were investigated by in situ X-ray diffraction (XRD). Orthorhombic (Pbcn) and monoclinic (C2/c) hydrides coexisted in the first absorption plateau, but only a monoclinic (C2/c) hydride was observed in the first desorption plateau. Phase transformation of La2Ni7H(x) was irreversible between the first as well as the second absorption-desorption process. The lattice parameters and expansion of the La2Ni4 and LaNi5 cells during the absorption-desorption process were refined using the Rietveld method. The lattice parameters a and b of the orthorhombic hydride (Pbcn) decreased, while the lattice parameter c increased with increasing hydrogen content in the first absorption. During the first absorption, the volume of the orthorhombic La2Ni4 cell expanded by more than 50%, while the expansion of the LaNi5 cell was below 10%. The monoclinic La2Ni4 cell expanded to approximately four times the size of the LaNi5 cell in the first absorption. The lattice parameters a, b, and c of the monoclinic hydride (C2/c) decreased with decreasing hydrogen content in the first desorption. These La2Ni4 and LaNi5 cells contracted isotropically in the first desorption.
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The hydrogen sorption properties of single-phase bcc (TiVNb)100-xCrx alloys (x = 0-35) are reported. All alloys absorb hydrogen quickly at 25 °C, forming fcc hydrides with storage capacity depending on the Cr content. A thermodynamic destabilization of the fcc hydride is observed with increasing Cr concentration, which agrees well with previous compositional machine learning models for metal hydride thermodynamics. The steric effect or repulsive interactions between Cr-H might be responsible for this behavior. The cycling performances of the TiVNbCr alloy show an initial decrease in capacity, which cannot be explained by a structural change. Pair distribution function analysis of the total X-ray scattering on the first and last cycled hydrides demonstrated an average random fcc structure without lattice distortion at short-range order. If the as-cast alloy contains a very low density of defects, the first hydrogen absorption introduces dislocations and vacancies that cumulate into small vacancy clusters, as revealed by positron annihilation spectroscopy. Finally, the main reason for the capacity drop seems to be due to dislocations formed during cycling, while the presence of vacancy clusters might be related to the lattice relaxation. Having identified the major contribution to the capacity loss, compositional modifications to the TiVNbCr system can now be explored that minimize defect formation and maximize material cycling performance.
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In situ gas-loading sample holders for two-dimensionally arranged detectors in time-of-flight neutron total scattering experiments have been developed to investigate atomic arrangements during deuterium absorption using time and real-space resolution. A single-crystal sapphire container was developed that allows conditions of 473â K and 10â MPa hydrogen gas pressure. High-resolution transient measurements detected deuterium absorption by palladium that proceeded within a few seconds. A double-layered container with thick- and thin-walled vanadium allowed conditions of 423â K and 10â MPa hydrogen gas pressure. The deuterium occupation sites of a lanthanum-nickel-aluminium alloy are discussed in detail on the basis of real-space high-resolution data obtained from in situ neutron scattering measurements and reverse Monte Carlo structural modeling.
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The intermetallic compound Pr(5)Ni(19), which is not shown in the Pr-Ni binary phase diagram, was synthesized, and the crystal structure was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Two superlattice reflections with the Sm(5)Co(19)-type structure (002 and 004) and the Pr(5)Co(19)-type structure (003 and 006) were observed in the 2θ region between 2° and 15° in the XRD pattern using Cu Kα radiation. Rietveld refinement provided the goodness-of-fit parameter S = 6.7 for the Pr(5)Co(19)-type (3R) structure model and S = 1.7 for the Sm(5)Co(19)-type (2H) structure model, indicating that the synthesized compound has a Sm(5)Co(19) structure. The refined lattice parameters were a = 0.50010(9) nm and c = 3.2420(4) nm. The high-resolution TEM image also clearly revealed that the crystal structure of Pr(5)Ni(19) is of the Sm(5)Co(19) type, which agrees with the results from Rietveld refinement of the XRD data. The P-C isotherm of Pr(5)Ni(19) in the first absorption was clearly different from that in the first desorption. A single plateau in absorption and three plateaus in desorption were observed. The maximum hydrogen storage capacity of the first cycle reached 1.1 H/M, and that of the second cycle was 0.8 H/M. The 0.3 H/M of hydrogen remained in the metal lattice after the first desorption process.
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Metal hydrides may play a paramount role in a future hydrogen economy. While most applications are based on nanostructured and confined materials, studies considering the structural response of these materials to hydrogen concentrate on bulk material. Here, using in situ in- and out-of-plane X-ray diffraction and reflectometry, we study the fcc â fct transition in Hf thin films, an optical hydrogen-sensing material. We show that the confinement of Hf affects this transition: compared to bulk Hf, the transition is pushed to a higher hydrogen-to-metal ratio, the tetragonality of the fct phase is reduced, and phase coexistence is suppressed. These nanoconfinement effects ensure the hysteresis-free response of hafnium to hydrogen, enabling its remarkable performance as a hydrogen-sensing material. In a wider perspective, the results highlight the profound influences of the nanostructuring and nanoconfinement of metal hydrides on their structural response to hydrogen with a significant impact on their applicability in future devices.
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Decades of research on solute-induced phase transformation of metal hydride systems have shown the possibility to enhance hydrogen storage properties through novel material design such as nanoconfinement engineering. Nevertheless, the fundamentals of mechanical stress effect on confined Pd nanoparticles remain yet to be elucidated due to the difficulty in linking with hydrogen sorption thermodynamics. Here, a thermodynamic tuning of Pd nanocubes associated with hydrogen sorption as a result of encapsulation by reduced graphene oxide (rGO) layers is demonstrated. Pd nanocubes are constrained by rGO to such a degree that the chemical potential and the pressure hysteresis of the system during hydrogen sorption drastically change while showing a size dependence. A thorough thermodynamic analysis elucidates the role of constraints on hydrogen uptake and release; despite the nanoscale regime, the thermodynamic parameters (enthalpy and entropy) during phase transition considerably increase, a phenomenon not seen before in unconstrained Pd nanoparticle systems.
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The phase transformation of La(2)Ni(7) during hydrogenation was investigated by in situ X-ray diffraction. We found two hydride phases, La(2)Ni(7)H(7.1) (phase I) and La(2)Ni(7)H(10.8) (phase II), during the first absorption cycle. The metal sublattice of phase I was orthorhombic (space group Pbcn) with lattice parameters a = 0.50128(6) nm, b = 0.8702(1) nm, and c = 3.0377(1) nm. The sublattice for phase II was monoclinic (space group C2/c) with lattice parameters a = 0.51641(9) nm, b = 0.8960(1) nm, c = 3.1289(1) nm, and ß = 90.17(1)°. The lattice parameter c increased with the hydrogen content, while a and b decreased in the formation of phase I from the alloy. Phase transformation from phase I to phase II was accompanied by isotropic expansion. The La(2)Ni(4) and LaNi(5) subunit expanded by 48.9% and 6.0% in volume, respectively, during hydrogenation to phase I. They expanded an additional 14% and 5.8%, respectively, in the formation of phase II. The obtained volume expansion suggested different hydrogen distribution in the La(2)Ni(4) and LaNi(5) subunit during hydrogenation.
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An energy-domain (57)Fe-Mössbauer spectrometer using synchrotron radiation (SR) with a diamond anvil cell (DAC) has been developed for ultrahigh-pressure measurements. The main optical system consists of a single-line pure nuclear Bragg reflection from an oscillating (57)FeBO(3) single crystal near the Néel temperature and an X-ray focusing device. The developed spectrometer can filter the Doppler-shifted single-line (57)Fe-Mössbauer radiation with a narrow bandwidth of neV order from a broadband SR source. The focused incident X-rays make it easy to measure a small specimen in the DAC. The present paper introduces the design and performance of the SR (57)Fe-Mössbauer spectrometer and its demonstrative applications including the newly discovered result of a pressure-induced magnetic phase transition of polycrystalline (57)Fe(3)BO(6) and an unknown high-pressure phase of Gd(57)Fe(2) alloy placed in a DAC under high pressures up to 302 GPa. The achievement of Mössbauer spectroscopy in the multimegabar range is of particular interest to researchers studying the nature of the Earth's core.
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Metal hydride (MH) actuators have a simple structure and a number of features that make them attractive for use in rehabilitation engineering and assistive technology. The MH actuator provides a high power-to-weight ratio, high-strain actuation, human-compatible softness, and noiseless operation, while being environmentally benign. On the other hand, there remain technical challenges to be overcome to improve the MH actuator regarding its speed of operation and energy efficiency, given the low heat conductivity of the MH powder that is used as the pressure generator for soft actuation. To overcome the issues of low heat conductivity and the handling of MH powder, we developed an MH paper, which is a special paper incorporating MH powder and carbon fiber, for use as a new pressure-generating element for a soft MH actuator system. In addition, the basic properties and structure of the proposed MH paper were investigated through scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and several thermodynamic experiments. The results of these experiments showed that the hydrogen absorption and desorption rates of the MH paper were significantly higher than those of the MH powder around room temperature.