High-pressure Form Research Articles

Improving electrochemical sodium storage performance and insight into the sodium ion diffusion in the high-pressure polymorph β-V2O5

The high-pressure form of vanadium pentoxide, β-V2O5, possesses promising sodium storage properties, featuring reversible sodium intercalation of one Na+ per formula unit, yielding an appealing capacity of 147 mAh g−1. However, its short cycle life in conventional carbonate-based electrolytes remains a significant drawback. In this work, we demonstrate that using non-carbonate-based electrolytes markedly enhances key electrochemical performances. Additionally, reducing the particle size of β-V2O5 through milling significantly increases the specific capacity, particularly at high current rates. Milled V2O5 maintains a respectable capacity of 73 mAh g−1 at 1 C rate, compared to the negligible capacity observed in non-milled V2O5. The milling process also alters the energy storage mechanism. Interestingly, after milling, sodium diffusion coefficient (DNa+) increased from 1.78 × 10−13 to 1.73 × 10−11 cm2 s−1, likely due to induced near-surface defects. Sodium storage exhibits dominant faradaic behavior at slow current rates, while, at high current rates, capacitive processes predominate. The synergy of improved sodium diffusion and additional capacitive charge storage leads to significantly improved electrochemical performance at high current rates. Furthermore, ionic liquid-based electrolytes promote long-life cycling, advancing this material toward practical application as a cathode in sodium-ion cells.

Fluid–solid coupled simulation of hypervelocity impact and plasma formation

Previous theoretical and computational studies on hypervelocity impact have mainly focused on the dynamic response of the solid materials that constitute the projectile and the target, while the surrounding environment is often assumed to be a vacuum. In this paper, we consider impact events that occur in a fluid (e.g., gas) medium, and present a computational model that includes the dynamics, thermodynamics, and ionization of the surrounding fluid material. The model couples the compressible Navier–Stokes equations with the Saha equations to predict the onset and extent of ionization in the surrounding fluid. An extended level set method with two signed distance functions is employed to track the three material interfaces between the projectile, the target, and the ambient fluid. This method accommodates the large deformation, contact, and separation of the interfaces, while avoiding spurious overlapping of different material subdomains. The advective fluxes across material interfaces are computed by constructing and solving bimaterial Riemann problems, thereby taking into account the discontinuities in both state variables (e.g., density) and thermodynamic relations. The computational model is first verified for an infinite ideal plasma and a one-dimensional three-material impact problem. Next, the model is employed to analyze the impact of a tantalum rod projectile onto a soda lime glass (SLG) target in an argon gas environment. In different analyses, the impact velocity is varied between 3 and 6km/s, and the radius of the projectile is varied between 2.5 and 10mm. Each analysis starts with a steady-state fluid dynamics simulation that generates the shock-dominated hypersonic flow around the projectile. This flow field is then used as an initial condition to start the fluid–solid coupled impact simulation. The predicted maximum temperature and pressure within the SLG target agree reasonably well with published experimental data for a similar material (fused quartz). Within the ambient gas, the impact-generated shock wave is found to be stronger than the initial bow shock in front of the projectile. Behind this shock wave, a region of high pressure and temperature forms in the early stage of the impact, mainly due to the hypersonic compression of the fluid between the projectile and the target. The temperature within this region is significantly higher than the peak temperature in the solid materials. For impact velocities higher than 4km/s, ionization is predicted. This finding indicates that the ambient gas may be a nontrivial contributor to the plasma formed in terrestrial and atmospheric hypervelocity impact events.

The Phase Diagram of the API Benzocaine and Its Highly Persistent, Metastable Crystalline Polymorphs.

The availability of sufficient amounts of form I of benzocaine has led to the investigation of its phase relationships with the other two existing forms, II and III, using adiabatic calorimetry, powder X-ray diffraction, and high-pressure differential thermal analysis. The latter two forms were known to have an enantiotropic phase relationship in which form III is stable at low-temperatures and high-pressures, while form II is stable at room temperature with respect to form III. Using adiabatic calorimetry data, it can be concluded, that form I is the stable low-temperature, high-pressure form, which also happens to be the most stable form at room temperature; however, due to its persistence at room temperature, form II is still the most convenient polymorph to use in formulations. Form III presents a case of overall monotropy and does not possess any stability domain in the pressure-temperature phase diagram. Heat capacity data for benzocaine have been obtained by adiabatic calorimetry from 11 K to 369 K above its melting point, which can be used to compare to results from in silico crystal structure prediction.

Is the impact sensitivity of RDX polymorph dependent?

Impact-sensitivity predictions based on the vibrational up-pumping model show a strong polymorph dependency for RDX and highlight that one of the high-pressure forms, which forms during shock-wave experiments, is appreciably more susceptible to mechanical initiation. The origin of the predicted impact sensitivity variation can be attributed to vibrational mode hardening by pressure and to differences in the molecular conformation of RDX in the four polymorphs studied. These polymorphs present different distributions of molecular vibrations within their respective up-pumping windows, which leads to their varying ability to up-pump and trap the vibrational energy that arises from mechanical insult.

The oscillatory effect of chemical constituents, dynamics, barometric, and thermodynamics on weather over Accra, and Bissau

A sharp contrast in atmospheric weather conditions prevailed over Accra and Bissau and that led to the oscillatory nature of weather conditions between the two cities. During the latter part of July 2022, Bissau experienced persistent and continuous rains whilst Accra remained fair and dry. It was realized that when an air parcel rises, low-pressure system is created at the surface but when the air parcel sinks, high pressure forms. Pressures were predominantly high over Accra and low over Bissau during that time. Models from CAMS were used to study chemical compositions to determine the concentration and effect of Sulphur Dioxide (SO2) over the two cities. Wind behavior over various levels in the atmosphere was considered using model products from ECMWF, satellite imagery from EUMETSAT, and t-phi gram from the Air Resources Laboratory of NOAA to study the thermodynamics of the skies. METAR, hourly observations made by the National Meteorological Offices from the two cities were retrieved from the AADS and Ogimet to study the barometric nature during the period. Results show that the atmosphere over Bissau had been less polluted as compared to that of Accra which makes Bissau to be persistently cloudy. Atmospheric chemical constituents would have to compete for moisture if the concentration is high and does not support the sustenance of massive clouds capable of producing rain. It has been realized that the development of anticyclone, an anticlockwise circulation at the 200 hPa level contributed to the cloud sustenance over Bissau during that time.

Electronic structure characterization of TiO2-II with the α-PbO2 structure by electron-energy-loss-spectroscopy and comparison with anatase, brookite, and rutile

TiO2-II is a high pressure form of titania with a density about 2% larger than that of rutile. In contrast to the common polymorphs anatase, brookite and rutile its electronic structure and optical properties are poorly characterized. Here we report on a comparative electron-energy-loss-spectroscopy (EELS) study for which high resolution valence-loss and core-loss EELS data were acquired from nanocrystalline (<75 ​nm sized) titania particles with an energy resolution of about 0.2 ​eV. Electronic structure features revealed from titanium L3,2 and oxygen K electron energy loss near-edge structures show a strong similarity of TiO2-II with both rutile and brookite, which is attributed to similarities in the connectivity of octahedral TiO6 units with neighboring ones. From combined valence-loss EELS and UV-VIS diffuse reflectance spectroscopy data the band gap of TiO2-II was determined to be indirect and with a magnitude of ∼3.18 ​eV, which is very similar to anatase (indirect, ∼3.2 ​eV), and distinctly different from rutile (direct, ∼3.05 ​eV) and brookite (direct, ∼3.45 ​eV).

High pressure behaviour of the organic semiconductor salt (TTF-BTD)2I3.

This study focuses on the effect of structure compression and cooling on the stereoelectronic properties of the planar π-conjugated TTF-BTD (TTF = tetrathiafulvalene; BTD = 2,1,3-benzothiadiazole) molecule, a prototypical example in which an electron-donor moiety is compactly annulated to an electron-acceptor moiety. Its partially oxidised iodine salt (TTF-BTD)2I3 is a crystalline semiconductor featuring segregated columns of TTF+0.5 units stacked via alternating short and long π-π interactions. We studied TTF-BTD at temperatures ranging from 300 K to 90 K and at pressures up to 7.5 GPa, using both X-ray diffraction and Raman spectroscopy to determine the properties of the compressed samples. Periodic DFT calculations and several theoretical tools were employed to characterize the calculated structural modifications and to predict the structural changes up to 60 GPa. The existence of an unprecedented new phase is predicted above 20 GPa, following a covalent bond formation between two neighbouring TTF-BTD units.

Atomic distribution and local structure in ice VII from in situ neutron diffraction

Ice polymorphs show extraordinary structural diversity depending on pressure and temperature. The behavior of hydrogen-bond disorder not only is a key ingredient for their structural diversity but also controls their physical properties. However, it has been a challenge to determine the details of the disordered structure in ice polymorphs under pressure, because of the limited observable reciprocal space and inaccuracies related to high-pressure techniques. Here, we present an elucidation of the disordered structure of ice VII, the dominant high-pressure form of water, at 2.2 GPa and 298 K, from both single-crystal and powder neutron-diffraction techniques. We reveal the three-dimensional atomic distributions from the maximum entropy method and unexpectedly find a ring-like distribution of hydrogen in contrast to the commonly accepted discrete sites. In addition, total scattering analysis at 274 K clarified the difference in the intermolecular structure from ice VIII, the ordered counterpart of ice VII, despite an identical molecular geometry. Our complementary structure analyses robustly demonstrate the unique disordered structure of ice VII. Furthermore, these findings are related to proton dynamics, which drastically vary with pressure, and will contribute to an understanding of the structural origin of anomalous physical properties of ice VII under pressures.

A Borosilicide with Clathrate VIII Structure.

The high-pressure phase Na8BxSi46–x (3 < x < 5) is the first representative of a borosilicide crystallizing in the rarely occurring clathrate VIII type structure. Crystals with composition Na8B4Si42 (space group I43̅m; a = 9.7187(2) Å; Pearson symbol cI54) were obtained at 5–8 GPa and 1200 K. The clathrate I modification exists for the same composition at lower pressure with a larger cell volume (Pm3̅n; a = 9. 977(2) Å; cP54). Profound structural adaptions allow for a higher density of the clathrate VIII type than clathrate I, opening up the perspective of obtaining clathrate VIII type compounds as high-pressure forms of clathrate I.

Unusual mechanical properties of ice VIII: Auxetic potential in a high pressure polymorph of ice

Water is known to have a complex phase diagram with numerous solid polymorphs, one of which is ice VIII, a proton ordered high pressure form of ice. In this work the mechanical properties of ice VIII were studied through the use of first principles density functional theory (DFT) simulations. In particular, it was shown that ice VIII has the potential of exhibiting a negative Poisson's ratio in the (110) plane on application of an on-axis stress. The auxetic behaviour of ice VIII was found to increase with an increase in hydrostatic pressure. This auxetic potential together with its pressure dependence was rationalised through the nanoscale deformation of this system when subjected to a series of stresses as well as through spectroscopic techniques. Our simulations suggest that the auxetic behaviour of ice VIII is due to the geometry of the oxygen sublattice in conjunction with an interplay between two deformation mechanisms namely stretching and hinging. As the hydrostatic pressure is increased the stretching mechanism becomes less significant resulting in the hinging mechanism becoming the predominate deformation mechanism.

Inorganic Structural Chemistry of Titanium Dioxide Polymorphs

Apart from rutile, which crystallizes in the rutile-type structure characteristic of many metal dioxides, three major polymorphs of titanium dioxide (TiO2) are known: anatase, brookite, and the α-lead dioxide (α-PbO2)-type high-pressure form. Ti ions are commonly found in octahedra composed of six oxide ions, and their crystal structures are distinguished according to the linkage pattern of the TiO6 octahedra. Inorganic structural chemistry considers that, in the rutile and α-PbO2 types, Ti ions occupy half of the octahedral voids in the hexagonal close packing of oxide ions, and the TiO6 octahedra in each layer are joined via edge sharing to form linear and zigzag strands, respectively. Anatase and brookite, on the other hand, exhibit more complex three-dimensional edge-sharing octahedral connections, although their origins are not fully explained. I show that these configurations can be interpreted as distinct stacking structures of layers with α-PbO2-type zigzag strands. Additionally, I characterize the crystal structures of four TiO2 polymorphs in detail using stacking sequence descriptions based on anion close packings and explore their relationships in terms of inorganic structural chemistry. I note that the moderate covalent nature of the Ti-O bond and the local structural instability of d0 ions result in an unusual variety of polymorphs in TiO2.

In situ study of calcite-III dimorphism using dynamic diamond anvil cell

The phase transitions among the high-pressure polymorphic forms of CaCO3 (cc-I, cc-II, cc-III, and cc-IIIb) are investigated by dynamic diamond anvil cell (dDAC) and in situ Raman spectroscopy. Experiments are carried out at room temperature and high pressures up to 12.8 GPa with the pressurizing rate varying from 0.006 GPa/s to 0.056 GPa/s. In situ observation shows that with the increase of pressure, calcite transforms from cc-I to cc-II at ∼ 1.5 GPa and from cc-II to cc-III at ∼ 2.5 GPa, and transitions are independent of the pressurizing rate. Further, as the pressure continues to increase, the cc-IIIb begins to appear and coexists with cc-III within a pressure range that is inversely proportional to the pressurizing rate. At the pressurizing rates of 0.006, 0.012, 0.021, and 0.056 GPa/s, the coexistence pressure ranges of cc-III and cc-IIIb are 2.8 GPa–9.8 GPa, 3.1 GPa–6.9 GPa, 2.7 GPa–6.0 GPa, and 2.8 GPa–4.5 GPa, respectively. The dependence of the coexistence on the pressurizing rate may result from the influence of pressurizing rate on the activation process of transition by reducing the energy barrier. The higher the pressurizing rate, the lower the energy barrier is, and the easier it is to pull the system out of the coexistence state. The results of this in situ study provide new insights into the understanding of the phase transition of calcite.

How many more polymorphs of ROY remain undiscovered.

With 12 crystal forms, 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecabonitrile (a.k.a. ROY) holds the current record for the largest number of fully characterized organic crystal polymorphs. Four of these polymorph structures have been reported since 2019, raising the question of how many more ROY polymorphs await future discovery. Employing crystal structure prediction and accurate energy rankings derived from conformational energy-corrected density functional theory, this study presents the first crystal energy landscape for ROY that agrees well with experiment. The lattice energies suggest that the seven most stable ROY polymorphs (and nine of the twelve lowest-energy forms) on the Z′ = 1 landscape have already been discovered experimentally. Discovering any new polymorphs at ambient pressure will likely require specialized crystallization techniques capable of trapping metastable forms. At pressures above 10 GPa, however, a new crystal form is predicted to become enthalpically more stable than all known polymorphs, suggesting that further high-pressure experiments on ROY may be warranted. This work highlights the value of high-accuracy crystal structure prediction for solid-form screening and demonstrates how pragmatic conformational energy corrections can overcome the limitations of conventional density functionals for conformational polymorphs.

Planetary Oceanography: Leveraging Expertise Among Earth and Planetary Science

The study of planetary oceanography is a new and exciting field of research. While humanity’s formal scientific studies of Earth’s ocean began nearly 150 years ago with the launch of the Challenger Expedition (Thomson et al., 1873), the study of oceans beyond Earth commenced only in this millennium. The first confirmation of an extensive saltwater ocean anywhere beyond Earth came relatively late within the lifetime of NASA’s Galileo mission (1989–2003; Kivelson et al., 2000), but continuing exploration has now revealed compelling evidence for large-volume watery oceans on five ice-covered moons of our outer solar system (Figure1), with as many as 10–20 candidate moons and dwarf planets also under consideration (Hendrix et al., 2019). Of the five confirmed ocean worlds (Jupiter’s moons Europa, Callisto, and Ganymede; Saturn’s moons Enceladus and Titan), three have oceans so deep that a high-pressure form of ice develops deep within the ocean, beneath the liquid water but overlying any rocky interior (Nimmo and Papallardo, 2016). As a consequence, the watery ocean is trapped within an “ice sandwich.” By contrast, the other two confirmed ocean worlds (Europa and Enceladus) have oceans that are in direct contact with a rocky interior.

Crystal structure of nyerereite: A possible messenger from the deep Earth

Abstract Carbonates in the system Na2CO3-CaCO3 are nowadays suggested as having a wide stability field at conditions of the mantle transition zone. Our structural analysis of nyerereite, which has limited stability fields at ambient conditions, and its similarities with already known carbonates that are stable at high-pressure conditions, allowed us to propose that nyerereite likely undergoes phase transitions at both high-pressure and high-temperature conditions. This supports the hypothesis that nyerereite takes part in carbon transportation from the mantle/deep crust toward the surface, with important implications for the deep carbon cycle associated with carbonatites. K-free nyerereite [Na2Ca(CO3)2] was synthesized both at hydrothermal conditions and from the melt. The structure of nyerereite was refined as a three-component twinned structure in the centrosymmetric Pbca space group with ratios of the three twinning components 0.221(3):0.287(3):0.492(3). Twinning at micro- and nano-level can introduce some minor structural deformations that influence the likely occurrence of the inversion center as one of the symmetry elements in the nyerereite structure. Based on the automated topological algorithms, we show that nyerereite has a unique crystal structure, not having analogs among the known structures, except for the structure with a similar composition K2Ca(CO3)2 fairchildite. A comparison between the centrosymmetric Pbca nyerereite structure and that of aragonite (CaCO3, Pmcn space group) reveals two main scenarios for the high-pressure form of Na2Ca(CO3)2: (1) poly-somatic relations as the interlayering of the high-pressure polymorph Na2CO3 and CaCO3-aragonite, and (2) high-pressure structure with ninefold-coordinated Na and Ca sites resembling that of aragonite. Our discussion heightens the interest in the high-pressure behavior of the nyerereite structure and strengthens the hypothesis about the possibility for nyerereite to be stable at high-pressure/high-temperature conditions.

High-pressure single-crystal synchrotron X-ray diffraction study of lillianite

Abstract In this paper, high-pressure data from a synchrotron X-ray diffraction study on a lillianite (Pb3Bi2S6) single crystal up to ~21 GPa are presented. A phase transition from lillianite (space group Bbmm, LP lillianite) to the high-pressure form β-Pb3Bi2S6 (space group Pbnm, HP lillianite) was confirmed and bracketed between 4.90 and 4.92 GPa. The transition is reversible but of first-order with a hysteresis of ~2.8 GPa. It showed weak effects of pseudo-merohedral twinning that disappeared upon decompression, testifying to a full recovery of the single crystal of lillianite. This makes lillianite an interesting shape-memory material. With a bulk modulus K4.9 = 78(3) GPa and K′ = 5.1(4), β-Pb3Bi2S6 is markedly less compressible than lillianite [K0 = 44(2) GPa, K′ = 7(1)]. Compressional anisotropy increases markedly in β-Pb3Bi2S6 with compressibility along the b axis [M0b = 130(6) GPa and Mb′ = 19(3) in lillianite, M4.9b = 145(4) GPa and Mb′ = 16.0(7) in β-Pb3Bi2S6] significantly larger than that along the other two axes [M0a = 118(5) GPa, Ma′ = 21(3), M0c = 139(12) GPa, and Mc′ = 31(10) in lillianite, M4.9a = 242(12) GPa, Ma′ = 8(1), M4.9c = 242(5) GPa, and Mc′ = 29(1) in β-Pb3Bi2S6]. The behavior of lillianite at high pressure is an interesting case study in relation to non-quenchable ultrahigh-pressure phases likely occurring in the inner Earth, like post-perovskite MgSiO3, the oxide homologue N = 1 of the lillianite series. The β-Pb3Bi2S6 structure, on the other hand, is the N = 3 homologue of the meneghinite series to which the higher-pressure modification of the post-perovskite structure also belongs (homologue N = 1). This makes the two forms of Pb3Bi2S6 potential equivalents of high- and ultrahigh-pressure Mg silicates that could occur both in the deep earth and in other rocky extrasolar planetary bodies.

Anomalous Volume Changes in the Siliceous Zeolite Theta-1 TON due to Hydrogen Insertion under High-Pressure, High-Temperature Conditions.

High-pressure X-ray diffraction and Raman spectroscopy in a diamond anvil cell were used to study the insertion of the chemical hydrogen storage material, ammonia borane, in the one-dimensional pores of the zeolite theta-1 TON. Heating of this material up to 300 °C under pressures up to 5 GPa resulted in the release of a significant amount of hydrogen due to the conversion of ammonia borane confined in the channels of TON and outside the zeolite to polyaminoborane and then polyiminoborane chains. The filling of TON with hydrogen resulted in a much greater increase in unit cell volume than that corresponding to thermal expansion of normal compact inorganic solids. This process at high temperature is accompanied by a phase transition from the collapsed high-pressure Pbn21 form to the more symmetric Cmc21 phase with expanded pores. This material has a high capacity for hydrogen adsorption under high-temperature, high-pressure conditions.

High Pressure Effect on Structural and Electrochemical Properties of Anionic Redox-Based Lithium Transition Metal Oxides

Summary The richness of anionic redox chemistry in the solid state offers new opportunities and a possible paradigm shift in energy storage. The excess capacity that goes beyond conventional theoretical values is attributed to the anionic redox in Li-rich transition metal oxide cathodes for Li-ion batteries. Their electrochemical behavior is thermodynamically determined by structural evolution. To better understand the electrochemical dependence on structural factors, we have induced structural modifications in pristine and electrochemically activated Li1.144Ni0.136Co0.136Mn0.544O2 through high-pressure treatment. A unique cyclical change of structural reordering is observed in the anionic redox-activated material during operando pressure sweep, characterized by a periodic evolution of superlattice peak intensity in synchrotron X-ray diffraction patterns. During the structural reordering period, the bulk compressibility of the material decreases, even becoming negative. These insights elucidate the structural flexibility and metastability of anionic redox-based materials, which can undergo large compressions and structural modifications while delivering good electrochemical properties.

High-pressure behaviour and phase stability of Ca2B6O6(OH)10·2(H2O) (meyerhofferite)

The high-pressure behaviour of meyerhofferite [ideally Ca2B6O6(OH)10·2(H2O), with a ~ 6.63 Å, b ~ 8.34 Å, c ~ 6.47 Å, α = 90.8°, β = 102°, γ = 86.8°, Sp. Gr. P\(\overline{1}\)], a B-bearing raw material (with B2O3 ≈ 46 wt%) and a potential B-rich aggregate, has been studied by single-crystal synchrotron X-ray diffraction up to 9 GPa, under hydrostatic conditions. Meyerhofferite undergoes a first-order phase transition to meyerhofferite-II, likely iso-symmetric, bracketed between 3.05 and 3.48 GPa, with a spectacular unit-cell volume discontinuity (i.e., ΔV ~ 30 Å3). The isothermal bulk modulus (KV0 = β−1P0,T0, where βP0,T0 is the volume compressibility coefficient) of meyerhofferite, was found to be KV0 = 31.6(5) GPa, and a marked anisotropic compressional pattern, with K(a)0: K(b)0: K(c)0 ~ 1.5:1:3, was observed. The bulk modulus of meyerhofferite-II increases to 55(2) GPa and, differently to the majority of the borates studied at high pressure so far, the anisotropic compressional pattern of meyerhofferite decreases markedly in the high-pressure form. The P-induced deformation mechanisms controlling, at the atomic scale, the bulk compression of meyerhofferite are here described. Considerations about the use of meyerhofferite as a potential B-based aggregate in concretes, mortars or resins, are provided.

Pressure-induced Esterification Reaction between Phosphoric Acid and Methanol

Esterification reaction between phosphoric acid and methanol proceeded markedly at 6 GPa and 25 °C. The yields of monomethyl phosphate and dimethyl phosphate were 17.0% and 0.3%, respectively. The yield of monomethyl phosphate at 6 GPa was at least 34 times higher than that under ambient conditions. The esterification reaction was accompanied by crystallization of ice VII, a high-pressure form of ice. It is likely that the formation of ice VII was the driving force of the esterification reaction.