Complex Phase Transitions Research Articles

Promoting Layered Oxide Cathodes Based on Structural Reconstruction for Sodium‐Ion Batteries: Reversible Phase Transition, Stable Interface Regulation, and Multifunctional Intergrowth Structure

AbstractLayered transition‐metal oxides (NaxTMO2) are one of the most promising cathode materials for sodium‐ion batteries due to their high theoretical specific capacities, good conductivity, and environmental friendliness. However, several key scientific issues of NaxTMO2 cathode materials still persist in practical applications: i) complex phase transitions during the charge/discharge process owing to the slip of the transition‐metal layer; ii) the tendency for the interface to react with the electrolyte, resulting in structure degradation, and iii) reactions between active materials and H2O as well as CO2 on exposure to air in the environment to form alkaline substances on the surface. To understand electrochemical storage mechanisms and solve these problems, several modification strategies of NaxTMO2 have been reported recently, including bulk doping, concentration gradient structure design, interface regulation, and intergrowth structure construction. This review focuses on reversible phase transitions, stable interface regulation, and multifunctional intergrowth structure of the NaxTMO2 material from the inside to the outside. The future research directions for NaxTMO2 are also analyzed, providing guidance for the development of commercial layered oxides for next‐generation energy storage systems.

Molecular Dynamics, Dielectric Properties, and Textures of Protonated and Selectively Deuterated 4'-Pentyl-4-biphenylcarbonitrile Liquid Crystal.

Using liquid crystals in near-infrared applications suffers from effects related to processes like parasitic absorption and high sensitivity to UV-light exposure. One way of managing these disadvantages is to use deuterated systems. The combined 1H and 2H nuclear magnetic resonance relaxometry method (FFC NMR), dielectric spectroscopy (DS), optical microscopy (POM), and differential scanning calorimetry (DSC) approach was applied to investigate the influence of selective deuteration on the molecular dynamics, thermal properties, self-organization, and electric-field responsiveness to a 4'-pentyl-4-biphenylcarbonitrile (5CB) liquid crystal. The NMR relaxation dispersion (NMRD) profiles were analyzed using theoretical models for the description of dynamics processes in different mesophases. Obtained optical textures of selectively deuterated 5CB showed the occurrence of the domain structure close to the I/N phase transition. The dielectric measurements showed a substantial difference in switching fields between fully protonated/deuterated 5CB and selectively deuterated molecules. The DSC thermograms showed a more complex phase transition sequence for partially deuterated 5CB with respect to fully protonated/deuterated molecules.

Effect of the position of Mg replacing Ni on O3-NaNi1/3Fe1/3Mn1/3O2 on the structural stability of cathode materials

O3-NaNi1/3Fe1/3Mn1/3O2 (NaNFM) materials are susceptible to complex phase transitions during electrical cycling leading to poor structural, capacity retention and multiplicity properties. These drawbacks hinder the application of NaNFM in sodium-ion batteries. Here, Mg2+ with larger ionic radius was used to dope its transition metal layer Ni site. The effects of Mg2+ doped NaNFM crystal structure and transition metal valence states on its electrochemical properties were investigated by XRD, SEM, and XPS. The capacity retention of NaNMFM-0.02 (84.05 %) was higher than that of NaNFM (73 %) after 200 cycles of the material at 5C. In addition, NaNMFM-0.02 achieved a first discharge specific capacity of 146.5 mAh/g at high voltage. Based on structural and electrochemical analyses, this improvement is attributed to the fact that magnesium acts as a “pillar” to stabilize the crystal structure of NaNFM, while magnesium doping reduces the Jahn-Teller effect. As a result, the material has better electrochemical properties.

Inhomogeneous Coordination in High-entropy O3-type Cathodes Enables Suppressed Slab Gliding and Durable Sodium Storage.

O3-type layered oxides are highly promising cathodes for sodium-ion batteries (SIBs), however they undergo complex phase transitions and exhibit high sensibility to air, leading to subpar cycling performance and commercial viability. In this work, we report a layered cathode material (NaNi0.29Cu0.1Mg0.05Li0.05Mn0.2Ti0.2Sn0.11O2) with a sate-of-the-art high-entropy compositional design. We unveil that such a configuration featuring inhomogeneous coordination environment of transition metal (TM) elements, can enable enhanced gliding energy (-0.38 vs -0.58 eV) of TMO2 slabs upon desodiation both theoretically and experimentally, which underlies the fundamental origin of the outstanding structural stability of HEO materials. As a consequence, the complex phase transitions (O3-O'3-P3-P'3-P3'-O3') of conventional O3-type cathode have been eliminated, and the as-obtained material demonstrates exceptional structural robustness and integrity with an ultra-long cycle life in a quasi-solid-state cell (maintaining 73.2% capacity after 1000 cycles at 2 C). Moreover, the material presents satisfactory air stability, with minimal structural and electrochemical degradation when directly exposed to the air. An Ah-scale pouch cell based on the cathode material is constructed, demonstrating a capacity retention of 83.6% after 500 cycles, signaling substantial promise for commercial applications.

Formation of hierarchically structured martensites in pure iron with ultrahigh strength and stiffness

Strong steels are primarily fabricated by introducing spatial obstacles (e.g., stacking faults and precipitates) that inhibit dislocation slips under stress to achieve high strength. However, for most low-carbon steels, such obstacles are difficult to form mainly because the martensitic transition is kinetically unfavorable by conventional methods, which precludes the attainment of high-strength materials in these steels with low solute contents. Here, we report an innovative high-pressure preparation of martensitic pure Fe with involving nano-effect, which leads to the formation of ultrastrong bulk iron with exceptionally high yield strength, ultimate strength, and hardness of 2.9 GPa, 3.7 GPa, and 9.0 GPa, respectively, exceeding those of high-speed steels. Such extraordinary mechanical properties are closely attributed to its high-density martensites with unique multiscale hierarchical structures formed due to complex phase transitions under pressure.

Interlayer substitution enables air-stable and long-life O3-type cathode for sodium-ion batteries

The O3-type oxides (NaNi0.4Fe0.2Mn0.4O2 (NFM)) have been considered as the most commercially cathode material for high-energy-density sodium-ion batteries owing to their low price, good safety performance, and high energy density. However, their further development is seriously limited due to the complex phase transition, sluggish kinetics of Na+, and intrinsic air instability. Herein, an interlayer substituted NFM (IS-NFM) is constructed by a simple solid-state method with the introduction of alkaline-earth metal. The interlayer substitution will lead to the increase of oxygen content in the internal lattice, which will effectively suppress the irreversible phase transition during cycling and exposure to the air. In addition, the interlayer substitution effectively activated the charge compensation, leading to the mobilized cationic redox process and boosted de-/sodiated kinetic. Consequently, IS-NFM exhibits excellent capacity retention of 83.44 % at 1 C after 200 cycles and remarkable stability even at high voltage. After 15 days of exposure to the air, IS-NFM also delivers superior capacity retention (86.53 %, compared with 0.1 C) and cycling performance (82.70 % at 1 C after 200 cycles). Undoubtedly, the interlayer substitution strategy will expand a novel avenue for constructing air-stable and long-life O3-type oxides for commercial application.

On the transition of liquid dispersion states and their physical-thermodynamic nature in the development of gas-condensate reservoirs in depletion mode

While the depletion regime for gas-condensate fields may be more cost-effective, it often results in the loss of hydrocarbon condensate, which is economically more valuable than gas, and leads to the inefficient exploitation of the field in terms of condensate production. Therefore, the development of effective exploitation systems for such fields is essential. Effective exploitation of gas-condensate fields involves achieving maximum hydrocarbon condensate production in addition to maximum gas production. From this aspect, managing the condensate factor of reservoir system during the depletion regime is a critical issue. The article experimentally and theoretically investigates the phase transitions or mutual dispersion occurrences between hydrocarbon liquid and gas mixtures that occur with a decrease in pressure at reservoir temperature during the natural depletion of gas-condensate fields. During the exploitation of gas-condensate fields, it has been observed that even at pressures higher than retrograde condensation pressure, the hydrocarbon system undergoes complex phase transitions, resulting in distinct transition points due to the mutual dispersion of hydrocarbon liquid and gas. Additionally, pVT studies conducted in the laboratory have made it possible to determine the transition points of the reservoir fluid in the “liquid in gas” and vice versa dispersion states. The research has demonstrated that dependance of gas condensate factor on pressure under given isothermal natural conditions more clearly reflects the retrograde and maximum condensation, also dispersion points of the liquid components. It was found that proportionality coefficient between condensate ratio and pressure of gas-condensate system is unique for each production facility under isothermal conditions and characterizes the stability of fluid’s dispersion state. The importance of considering such transition points when designing gas-condensate field development projects has been highlighted.

Complex Phase Transitions of Fully Rigid Sphere-Rod Amphiphiles Induced by Solvent Polarity in Dilute Solutions.

We report complex macrophase and microphase transitions of rigid amphiphiles with spherical Keggin molecular clusters as the solvophilic block and rod-like rigid oligofluorene (OF) as the solvophobic block in mixed solvents of water and polar organic solvent. By properly adjusting the solvent polarity, the amphiphiles are found to respond accordingly by self-assembling into multilayered incomplete onion-like structures (10-25 vol % THF), single-layered vesicular structures (60 vol % THF), and an unexpected macrophase separation in the middle (40-50 vol % THF), which is due to the anomalous trends in Keggin solubility as a result of the nature of TBA+ counterions. The rigidity of the OF block prevents the amphiphile from assembling by following the rule of packing parameters; instead, interdigitation among different rods leads to the formation of the solvophobic domain to achieve self-assembly. The incomplete onion structures are controlled by the interdigitation of rigid rods for the number of layers and the electrostatic interaction among Keggin head groups for the interlayer distance. When the degree of interdigitation becomes lower, the self-assembly process shows a trend that can be explained by the traditional rule of packing parameter. This study demonstrates the formation of different self-assembled structures by rigid amphiphiles and their transitions induced by solvent composition. The self-assembly (microphase separation) of rigid amphiphiles in a dilute solution could indeed represent a broad area containing complicated, uncharted rules.

Phase diagram of strongly-coupled Rashba systems

Abstract Motivated by the recent discovery of a possible field-mediated parity switch within the superconducting state of CeRh2As2 [Khim et al., Science 373, 1012 (2021)], we thoroughly investigate the dependence of the superconducting state of a strongly-coupled Rashba mono- and bilayer on internal parameters and an applied magnetic field. The role of interlayer pairing, spin orbit coupling, doping rate and applied magnetic field and their interplay was examined numerically at low temperature within a t-J-like model, uncovering complex phase diagrams and transitions between superconducting states with different symmetry.

A high-entropy cathode for sodium-ion batteries: Cu/Zn-doping O3-Type Ni/Fe/Mn layer oxides

The O3 layered oxides have been extensively investigated as cathode materials for sodium-ion batteries due to their remarkable theoretical capacity. However, the large radius of Na+ lead to complex phase transitions and tortuous diffusion channels during extraction/insertion, which ultimately restricts the Na+ diffusion kinetics and cyclic stability. In this study, we report a Zn and Cu co-doping strategy to the high entropy layer oxide Na [Ni0·2Fe0·2Mn0·4Cu0·15Zn0.05]O2 (HEO-CuZn) using the sol-gel method to prepare the oxides. Here, Zn is used to stabilize the structure of layer between the transition metal and O atoms, which slows down the adverse phase transition. In the fabricated sample, the element Cu provides additional capacity and inhibits excessive oxidation. The prepared HEO-CuZn used as cathode for Na+ ion battery exhibits better electrochemical performance, delivering a high specific capacity of 148 mA h g−1, and 84 % capacity retention after 100 cycles, which is attributed to the expanded Na+ transfer channels, reduced activation energy and interface side reactions, thus enhancing the Na+ diffusion kinetics. Meanwhile, the high entropy strategy stabilizes the overall structure by reducing the John-Teller distortion and suppressing the Na+/vacancy order, and effectively avoids adverse phase transitions such as O′3 and P′3. This study provides a new insight for the advance of the next generation high specific energy sodium-ion battery.

Air-Stable High-Entropy Layered Oxide Cathode with Enhanced Cycling Stability for Sodium-Ion Batteries.

O3-type layered oxides have been extensively studied as cathode materials for sodium-ion batteries due to their high reversible capacity and high initial sodium content, but they suffer from complex phase transitions and an unstable structure during sodium intercalation/deintercalation. Herein, we synthesize a high-entropy O3-type layered transition metal oxide, NaNi0.3Cu0.05Fe0.1Mn0.3Mg0.05Ti0.2O2 (NCFMMT), by simultaneously doping Cu, Mg, and Ti into its transition metal layers, which greatly increase structural entropy, thereby reducing formation energy and enhancing structural stability. The high-entropy NCFMMT cathode exhibits significantly improved cycling stability (capacity retention of 81.4% at 1C after 250 cycles and 86.8% at 5C after 500 cycles) compared to pristine NaNi0.3Fe0.4Mn0.3O2 (71% after 100 cycles at 1C), as well as remarkable air stability. Finally, the NCFMMT//hard carbon full-cell batteries deliver a high initial capacity of 103 mAh g-1 at 1C, with 83.8 mAh g-1 maintained after 300 cycles (capacity retention of 81.4%).

Cu-substituted Na0.75Ni0.17Cu0.08Mn0.75O2 cathode with suppressing P2-O2 phase transition and air-stable for high-performance sodium-ion batteries

P2-Na0.75Ni0.25Mn0.75O2 cathode material with high specific capacity and high operating voltage is favored by researchers. However, the complex phase transition (P2-O2) at high voltage and the rapid capacity decay caused by Na+/vacancy ordering seriously restrict its application. In this study, a series of Cu-substituted P2-type Na0.75Ni0.25-xCuxMn0.75O2 (x = 0, 0.02, 0.04, 0.06, 0.08, 0.1) cathodes are synthesized. The Na0.75Ni0.17Cu0.08Mn0.75O2 cathode achieves a high initial discharge capacity of 133.6 mAh g−1 and remains 80.5 % of this capacity after 150 cycles at 0.1C, outperforming the performance of other compositions. Investigations into the superior electrochemical performance of Na0.75Ni0.17Cu0.08Mn0.75O2 through a multi-technique approach, including in-situ X-ray diffraction (XRD), ex-situ X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT), elucidate the underlying mechanisms. The results show that the introduction of Cu2+ in Na0.75Ni0.25Mn0.75O2 can successfully regulate the ratio of Naf/Nae, with enhanced cell performance when Na+ occupies more Nae sites compared to Naf sites. In-situ XRD confirms that the Cu substitution for Ni stabilizes the P2 structure during the charge–discharge process and inhibits the unfavorable P2-O2 phase transition at high voltage. In addition, Cu-substituted cathode materials exhibit a good effect on improving air stability, attributed to the higher Cu2+/Cu3+ redox potential. This unique substitution mechanism offers a novel perspective for understanding the structure-performance relationship of P2-type cathode materials and provides important support for the design of air-stable, high-performance cathode materials.

Thermo-poroelastic AVO modeling of Olkaria geothermal reservoirs

Seismic AVO has a significant potential for fluid identification in time-lapse monitoring of the cyclic recovery of geothermal reservoirs. With this goal, we develop an AVO method based on the reflection and transmission (R/T) of elastic waves at an interface between two fluid-saturated thermo-poroelastic media. The method is applied to the Olkaria geothermal reservoir modeling in Kenya. This system is characteristic of a natural cyclic recovery, where cyclic meteoric water undergoes complex phase transition and thermo-hydro-mechanical coupling process. Conceptual models are built based on petrophysical and thermophysical properties of trachyte thermal reservoirs, and the fluid properties under different temperature conditions have been considered. A plane-wave analysis illustrates the effects of thermal conductivity, specific heat, and porosity on velocity dispersion and attenuation of the fast-P, Biot P, and thermal P waves. AVO modeling by P-wave incidence is conducted to investigate the effects of temperature, porosity, and fluid type on the R/T coefficients. For trachyte reservoirs with a temperature less than 500 °C, limited changes in the thermophysical properties have negligible effects on wave propagation, whereas significant effects are due to temperature, porosity, and fluid type. Synthetic seismogram also indicates that the thermo-poroelastic effect noticeable changes the seismic responses compared with the traditional elastic and thermoelastic models. The thermo-poroelastic AVO method proposed in this paper reveals the variation of R/T coefficients of geothermal reservoirs under different conditions. The results can be used as a precursor to geothermal reservoir monitoring, fluid leakage or short circuits.

Physical Properties of CaTiO3-Modified NaNbO3 Thin Films.

NaNbO3(NN)-based lead-free materials are attracting widespread attention due to their environment-friendly and complex phase transitions, which can satisfy the miniaturization and integration for future electronic components. However, NN materials usually have large remanent polarization and obvious hysteresis, which are not conducive to energy storage. In this work, we investigated the effect of introducing CaTiO3((1-x)NaNbO3-xCaTiO3) on the physical properties of NN. The results indicated that as x increased, the surface topography, oxygen vacancy and dielectric loss of the thin films were significantly improved when optimal value was achieved at x = 0.1. Moreover, the 0.9NN-0.1CT thin film shows reversible polarization domain structures and well-established piezoresponse hysteresis loops. These results indicate that our thin films have potential application in future advanced pulsed power electronics.

Deep insight on Li interlayer migration in O3-type NaLi1/3Mn2/3O2 as a cathode material for Na-ion batteries

Layered manganese transition metal oxides, such as NaMnO2, have attracted great interest due to the low cost and high capacity. However, complex phase transitions in NaMnO2 lead to poor cycling stability. The introduction of Li doping has been confirmed to improve the performance of NaMnO2. O3-type NaLi1/3Mn2/3O2 (NLMO), synthesized in 2021, has demonstrated excellent electrochemical performance. Notably, irreversible Li interlayer migration (Li migrates from the transition metal layer to the alkali metal layer) has been observed during cycling, which is related to the electrochemical performance. Therefore, it is crucial to understand the mechanism underlying Li interlayer migration in O3-NLMO. However, the environment of Li interlayer migration on cycling is complex and involves interlayer spacing, Na-ion concentration, the degree of O-ion oxidation, and phase transition. Here, in this work, we utilized the first-principles method to decouple the coupling factors influencing the Li interlayer migration. Through analyzing the impact of the single-factor on Li interlayer migration, we aim to identify the crucial factors affecting this process. Our results show that a decrease in Na-ion concentration and an increase in O-ion oxidation degree promote the Li interlayer migration, while the O–P phase transition suppresses the Li interlayer migration. Interlayer spacing was found to play a less influential role in Li interlayer migration. Our investigations provide effective strategies for the subsequent regulation of Li interlayer migration.

High‐entropy configuration strategy boosts excellent rate performance of layered oxide for sodium‐ion batteries

AbstractLayered oxides are considered to be potential cathodes for sodium‐ion batteries based on high theoretical capacity and ease of synthesis. However, the complex phase transition caused by interlayer sliding in layered oxides leads to poor cycling stability, which will hinder their further application. Here, we designed a newly O3‐type layered cathode NaNi0.3Co0.2Cu0.1Mn0.2Ti0.2O2 based on high‐entropy to achieve highly reversible phase transition behavior. It reveals 132 mAh g−1 at 0.2 C within 2–4 V increasing the energy density to 408 Wh kg−1 and it shows an outstanding rate capability of 90 mAh g−1 at 80 C (84.90% capacity retention after 1,500 cycles at 80 C). In‐situ XRD shows that reasonable design of high‐entropy components in layered material can achieve the purpose of delaying the occurrence of phase transition and DFT calculations show that the introduction of Co in transition metal layers can effectively improve the rate performance of the material. This work is of great significance in guiding the design and synthesis of highly stable layered cathode materials for sodium‐ion batteries.

Deviatoric stress-induced metallization, layer reconstruction and collapse of van der Waals bonded zirconium disulfide

In contrast to two-dimensional (2D) monolayer materials, van der Waals layered transition metal dichalcogenides exhibit rich polymorphism, making them promising candidates for novel superconductor, topological insulators and electrochemical catalysts. Here, we highlight the role of hydrostatic pressure on the evolution of electronic and crystal structures of layered ZrS2. Under deviatoric stress, our electrical experiments demonstrate a semiconductor-to-metal transition above 30.2 GPa, while quasi-hydrostatic compression postponed the metallization to 38.9 GPa. Both X-ray diffraction and Raman results reveal structural phase transitions different from those under hydrostatic pressure. Under deviatoric stress, ZrS2 rearranges the original ZrS6 octahedra into ZrS8 cuboids at 5.5 GPa, in which the unique cuboids coordination of Zr atoms is thermodynamically metastable. The structure collapses to a partially disordered phase at 17.4 GPa. These complex phase transitions present the importance of deviatoric stress on the highly tunable electronic properties of ZrS2 with possible implications for optoelectronic devices.

Three-dimensional hidden phase probed by in-plane magnetotransport in kagome metal CsV3Sb5 thin flakes

Transition metal compounds with kagome structure have been found to exhibit a variety of exotic structural, electronic, and magnetic orders. These orders are competing with energies very close to each other, resulting in complex phase transitions. Some of the phases are easily observable, such as the charge density wave (CDW) and the superconducting phase, while others are more challenging to identify and characterize. Here we present magneto-transport evidence of a new phase below ~ 35 K in the kagome topological metal CsV3Sb5 (CVS) thin flakes between the CDW and the superconducting transition temperatures. This phase is characterized by six-fold rotational symmetry in the in-plane magnetoresistance (MR) and is connected to the orbital current order in CVS. Furthermore, the phase is characterized by a large in-plane negative magnetoresistance, which suggests the existence of a three-dimensional, magnetic field-tunable orbital current ordered phase. Our results highlight the potential of magneto-transport to reveal the interactions between exotic quantum states of matter and to uncover the symmetry of such hidden phases.

Multiphase manganese-based layered oxide for sodium-ion batteries: structural change and phase transition

Sodium-ion batteries (SIBs) are recognized as a leading option for energy storage systems, attributed to their environmental friendliness, natural abundance of sodium, and uncomplicated design. Cathode materials are crucial in defining the structural integrity and functional efficacy of SIBs. Recent studies have extensively focused on manganese (Mn)-based layered oxides, primarily due to their substantial specific capacity, cost-effectiveness, non-toxic nature, and ecological compatibility. Additionally, these materials offer a versatile voltage range and diverse configurational possibilities. However, the complex phase transition during a circular process affects its electrochemical performance. Herein, we set the multiphase Mn-based layered oxides as the research target and take the relationship between the structure and phase transition of these materials as the starting point, aiming to clarify the mechanism between the microstructure and phase transition of multiphase layered oxides. Meanwhile, the structure-activity relationship between structural changes and electrochemical performance of Mn-based layered oxides is revealed. Various modification methods for multiphase Mn-based layered oxides are summarized. As a result, a reasonable structural design is proposed for producing high-performance SIBs based on these oxides.

Krylov complexity and dynamical phase transition in the quenched Lipkin-Meshkov-Glick model

Krylov complexity and dynamical phase transition in the quenched Lipkin-Meshkov-Glick model