Structural Evolution Research Articles

Dynamics and Internal Structure Evolution during the Glass Transition of the Ethylene-Cyclic Olefin Copolymers: A Molecular Dynamics Simulation.

Amorphous ethylene-cyclic olefin copolymers (COCs) which can be used in cell phone lenses and prefilled syringes have attracted increasing attention due to their excellent and tunable thermal properties. In order to better explain the influence of COC microstructure (cyclic olefin types and content) on the glass transition mechanism, we used molecular dynamics (MD) simulations to track the evolution of free volume, diffusion coefficients, atomic mobility, trans conformation probabilities, and characteristic parameters of α-relaxation kinetics during the quenching process. MD results show that for the classic COC E-co-NB (ethylene-norbornene copolymer), an increase in cyclic olefin content from 25 to 50 mol % reduces atomic mobility, limiting the molecular chain movement at higher temperatures and improving Tg. Compared to NB, the more rigid rings in tricyclopentadiene (TCPD) and exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-bridged phenylidene-1,4-bridged methylideneanthracene (HBM) have the following effects: (1) reducing the thermal expansion coefficient and overall chain mobility; (2) enhancing the diffusion energy barrier; (3) promoting the formation of local ordered structures; (4) accelerating α-relaxation dynamics at high temperatures and improving the dynamic fragility m. These lead to an upward shift in the temperature region where chain movement is limited and thus improve Tg and high-temperature dimensional stability. In this simulation, the correlation equation between Tg, m, and the microstructural parameters of COCs is established, which is of great significance for the development of COCs with high performance.

Neural network kinetics for exploring diffusion multiplicity and chemical ordering in compositionally complex materials

Diffusion involving atom transport from one location to another governs many important processes and behaviors such as precipitation and phase nucleation. The inherent chemical complexity in compositionally complex materials poses challenges for modeling atomic diffusion and the resulting formation of chemically ordered structures. Here, we introduce a neural network kinetics (NNK) scheme that predicts and simulates diffusion-induced chemical and structural evolution in complex concentrated chemical environments. The framework is grounded on efficient on-lattice structure and chemistry representation combined with artificial neural networks, enabling precise prediction of all path-dependent migration barriers and individual atom jumps. To demonstrate the method, we study the temperature-dependent local chemical ordering in a refractory NbMoTa alloy and reveal a critical temperature at which the B2 order reaches a maximum. The atomic jump randomness map exhibits the highest diffusion heterogeneity (multiplicity) in the vicinity of this characteristic temperature, which is closely related to chemical ordering and B2 structure formation. The scalable NNK framework provides a promising new avenue to exploring diffusion-related properties in the vast compositional space within which extraordinary properties are hidden.

High-Voltage Spinel Cathode Materials: Navigating the Structural Evolution for Lithium-Ion Batteries.

High-voltage LiNi0.5Mn1.5O4 (LNMO) spinel oxides are highly promising cobalt-free cathode materials to cater to the surging demand for lithium-ion batteries (LIBs). However, commercial application of LNMOs is still challenging despite decades of research. To address the challenge, the understanding of their crystallography and structural evolutions during synthesis and electrochemical operation is critical. This review aims to illustrate and to update the fundamentals of crystallography, phase transition mechanisms, and electrochemical behaviors of LNMOs. First, the research history of LNMO and its development into a LIB cathode material is outlined. Then the structural basics of LNMOs including the classic and updated views of the crystal polymorphism, interconversion between the polymorphs, and structure-composition relationship is reviewed. Afterward, the phase transition mechanisms of LNMOs that connect structural and electrochemical properties are comprehensively discussed from fundamental thermodynamics to operando dynamics at intra- and inter-particle levels. In addition, phase evolutions during overlithiation as well as thermal-/electrochemical-driven phase transformations of LNMOs are also discussed. Finally, recommendations are offered for the further development of LNMOs as well as other complex materials to unlock their full potential for future sustainable and powerful batteries.

Effect of Obstacle Gradient on the Deflagration Characteristics of Hydrogen/Air Premixed Flame in a Closed Chamber

In this paper, computational fluid dynamics (CFD) numerical simulation is employed to analyze and discuss the effect of obstacle gradient on the flame propagation characteristics of premixed hydrogen/air in a closed chamber. With a constant overall volume of obstacles, the obstacle blocking rate gradient is set at +0.125, 0, and −0.125, respectively. The study focuses on the evolution of the flame structure, propagation speed, the dynamic process of overpressure, and the coupled flame–flow field. The results demonstrate that the flame front consistently maintains a jet flame as the obstacle gradient increases, with the wrinkles on the flame front becoming increasingly pronounced. When the blocking rate gradients are +0.125, 0, and −0.125, the corresponding maximum flame propagation speeds are measured at 412 m/s, 344 m/s, and 372 m/s, respectively, indicating that the obstacle gradient indeed increases the flame propagation speed. Moreover, the distribution of pressure is closely related to changes in the flame structure, with the overpressure decreasing in the obstacle channel as the obstacle gradient increases. Furthermore, the velocity vector and vortex distribution in the flow field are revealed and compared. It is found that the obstacle tail vortex is the main factor inducing flame evolution and flow field changes in a closed chamber. The effect of the blocking rate gradient on flow velocity is also quantified, with instances of deceleration occurring when the blocking rate gradient is −0.125.

Balanced Mass Transfer and Active Sites Density in Hierarchical Porous Catalytic Metal-Organic Framework for Enhancing Redox Reaction in Lithium-Sulfur Batteries.

Developing highly efficient catalysts, characterized by controllable pore architecture and effective utilization of active sites, is paramount in addressing the shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs) in lithium-sulfur batteries (LSBs), which, however, remains a formidable challenge. In this study, a hierarchical porous catalytic metal-organic framework (HPC-MOF) with both appropriate porosity and abundant exposed catalytic sites is achieved through time-controlled precise pore engineering. It is revealed that the evolution of the porous structure and catalytic site density is time-dependent during the etching processes. The moderately etched HPC-MOF-M attains heterogeneous pores at various scales, where large apertures ensure fast mass transfer and micropores inherit high-density catalytic sites, enhancing utilization and catalytic kinetics at internal catalytic sites. Capitalizing on these advantages, LSB incorporating the HPC-MOF-M interlayer demonstrates a 164.6% improvement in discharge capability and an 83.3% lower decay rate over long-term cycling at 1.0C. Even under high sulfur loading of 7.1 mg cm-2 and lean electrolyte conditions, the LSB exhibits stable cycling for over 100 cycles. This work highlights the significance of balancing the relationship between mass transfer and catalytic sites through precise chemical regulation of the porous structure in catalytic MOFs, which are anticipated to inspire the development of advanced catalysts for LSBs.

Tailored Metal-Organic Frameworks for Water Purification: Perfluorinated Fe-MOFs for Enhanced Heterogeneous Catalytic Ozonation.

An industrially viable catalyst for heterogeneous catalytic ozonation (HCO) in water purification requires the characteristics of good dispersion of active species on its surface, efficient electron transfer for ozone decay, and maximum active species utilization. While metal-organic frameworks (MOFs) represent an attractive platform for HCO, the metal nodes in the unmodified MOFs exhibit low catalytic activity. Herein, we present a perfluorinated Fe-MOF catalyst by substituting H atoms on the metalated ligands with F atoms (termed 4F-MIL-88B) to induce structure evolution. The Lewis acidity of 4F-MIL-88B was enhanced via the formation of Fe nodes, tailoring the electron distribution on the catalyst surface. As a result of catalyst modification, the rate constant for degradation of the target compounds examined increased by ∼700% compared with that observed for the unmodified catalyst. Experimental evidence and theoretical calculations showed that the modulated polarity and the enhanced electron transfer between the catalyst and ozone molecules contributed to the adsorption and transformation of O3 to •OH on the catalyst surface. Overall, the results of this study highlight the significance of tailoring the metalated ligands to develop highly efficient and stable MOF catalysts for HCO and provide an in-depth mechanistic understanding of their structure-function evolution, which is expected to facilitate the applications of nanomaterial-based processes in water purification.

Investigating the equation-of-state, stability and mass–radius relationship of anisotropic and massive neutron stars embedded in f(R,T) modified gravity

In this study, our main focus is to investigate the mass–radius relation and several important properties of massive neutron stars to realize the nature, behavior and evolution of these kinds of compact objects at present time. Also, we want to understand the equation-of-state of the core nuclear matter precisely with their stable equilibrium configuration. We have chosen a few massive binary pulsars and investigated on maximum attainable mass and lowest possible radius of them. We have considered Einstein–Hilbert action as [Formula: see text], where [Formula: see text] is the Ricci scalar and [Formula: see text], the trace of energy–momentum tensor with [Formula: see text] as the coupling parameter and also used modified TOV equations. The interior space-time of the spherical neutron star is matched to the exterior Schwarzschild line element at the surface of the star. The [Formula: see text]–[Formula: see text] curve can predict the maximum achievable mass is about [Formula: see text] with lowest possible radius of around [Formula: see text] km for the massive compact stars under stable equilibrium. We have obtained a clear picture of structural evolution of massive neutron stars through accelerating space-time and can put some constraints on several quantities related to them. It is depicted from our present investigation that all the derived outcomes are compatible with physically adopted regimes which reveal the viability of our current model in the context of [Formula: see text] modified gravity.

2D Hybrid Perovskites: From Static and Dynamic Structures to Potential Applications.

2D perovskites have received great attention recently due to their structural tunability and environmental stability, making them highly promising candidates for various applications by breaking property bottlenecks that affect established materials. However, in 2D perovskites, the complicated interplay between organic spacers and inorganic slabs makes structural analysis challenging to interpret. A deeper understanding of the structure-property relationship in these systems is urgently needed to enable high-performance tunable optoelectronic devices. Herein, this study examines how structural changes, from constant lattice distortion and variable structural evolution, modeled with both static and dynamic structural descriptors, affect macroscopic properties and ultimately device performance. The effect of chemical composition, crystallographic inhomogeneity, and mechanical-stress-induced static structural changes and corresponding electronic band variations is reported. In addition, the structure dynamics are described from the viewpoint of anharmonic vibrations, which impact electron-phonon coupling and the carriers' dynamic processes. Correlated carrier-matter interactions, known as polarons and acting on fine electronic structures, are then discussed. Finally, reliable guidelines to facilitate design to exploit structural features and rationally achieve breakthroughs in 2D perovskite applications are proposed. This review provides a global structural landscape of 2D perovskites, expected to promote the prosperity of these materials in emerging device applications.

Exceeding Three-Electron Reactions in Polyanionic Cathode To Achieve High-Energy Density for Sodium-Ion Batteries.

Activating multielectron reactions of sodium superionic conductor (NASICON)-type cathodes toward higher energy density remains imperative to boost their application feasibility. However, multisodium storage with high stability is difficult to achieve due to the sluggish reaction kinetics, irreversible phase transitions, and negative structural degradation. Herein, a kind of NASICON-type Na2.5V1.5Ti0.5(PO4)3/C (NVTP-0.5) hierarchical microsphere consisting of abundant primary nanoparticles is designed, realizing a reversible 3.2-electron reaction with high stability. The optimized NVTP-0.5 cathode demonstrates an ultrahigh discharge capacity of 192.42 mAh g-1, energy density of up to 497.3 Wh kg-1 at 20 mA g-1, and capacity retention ratio of 94.1% after 1000 cycles at 1 A g-1. Additionally, the NVTP-0.5 cathode delivers excellent tolerance to extreme temperatures while also achieving a high-energy density of 400 Wh kg-1 (based on the cathode mass) in a full-cell configuration. Systematic in situ/ex situ analysis results confirm the multisodium storage processes of NVTP-0.5 involving successive redox reactions (V2+/V3+, Ti3+/Ti4+, and V3+/V4+ redox couples) and reversible structure evolution (solid-solution and biphasic mechanisms), which contribute to the high capacity and excellent cycling stability. This work indicates that the rational regulation of components with different functions can unlock more possibilities for the development of NASICON-type cathodes.

Interfacial molecular structure and orientation evolution of the polystyrene under confinement during annealing revealed by sum frequency generation vibrational spectroscopy

The geometrical confinement directly affects many crucial properties of polymer thin films by interfacial interactions. A key to understanding the role of these interfacial interactions is to specifically probe the confined interface at the molecular level and in situ. However, the direct and nondestructive detection of interfacial polymer structures under confinement is very difficult. In this study, specific interface-sensitive sum frequency generation (SFG) spectroscopy was applied to study the deuterated PS (d8-PS) film confined between hydrogenated poly (methyl methacrylate) (PMMA) films at the molecular level and in situ. The results showed that the ordering/orientation of the PS chain (backbone and phenyl group) evolved at the buried d8-PS/PMMA interface during annealing. The tilt angle of the PS phenyl group increased while the twist angle decreased with elevated annealing temperature. Both overall SFG ssp and ppp intensities decreased after annealing at 433 K for 24 h, indicating that PS chains entangled with or penetrated the PMMA chains at the confined interface. This study qualitatively and quantitatively revealed the interfacial structure and structural evolution of the PS chain confined between PMMA films in situ during annealing, which is beneficial to the molecular-level understanding of the interfacial chain conformational relaxation of polymers under confinement.

From cement to geopolymers: Performances and sustainability advantages of ambient curing

The production of Portland cement results in substantial carbon emissions. Geopolymers are regarded as highly promising alternative binder materials to cement due to their low energy consumption and excellent mechanical properties. However, it should be noted that the thermal curing process of geopolymers diminishes their low-carbon advantage. In this study, ground granulated blast furnace slag (GGBS) was used to replace metakaolin (MK) by the ratio of 10 %, 20 %, 30 %, 40 %, and 50 % to produce geopolymers. The aim was to examine the impact of GGBS content on the thermal curing performance of MK-based geopolymers. The microstructure of the specimens was analyzed using SEM and XRD analysis techniques. Lastly, a comprehensive assessment of their sustainability potential was carried out. As a result, slag may increase flow spread, decrease the setting time, and effectively improve the mechanical properties which curing on ambient temperature. The group with 50 % slag content had the highest compressive and flexural strengths, reaching 55.9 MPa and 8.45 MPa at 28 d, respectively. The drying shrinkage of geopolymers increases as the GGBS content goes up. Notably, owing to the evolution of chemical transformation and gel structure, MK exhibits a significant mitigation on shrinkage. Ultimately, with a 50 % slag content, the carbon dioxide emissions of geopolymer can be reduced to 265.36 kg CO2-eq, which is a 43.6 % decrease compared to that of OPC. With a comprehensive consideration of the performance and sustainability potential of geopolymers, it is recommended to introduce GGBS content in the range of 30 %–40 %.

A Bibliometric Review on Deoxyribonucleic Acid (DNA) Splicing System

This study objects to provide a communicative review for splicing system, focusing on deoxyribonucleic acid (DNA) published in journals and proceedings indexed by the Scopus database. The method of bibliometric analysis is used to describe and analyze the evolution of publication structure and its various co-relationships such as citation, co-citation, co-authorship, and co-occurrence, among the chosen 174 documents indexed by Scopus. This study gives some insightful direction of research where the most influential documents and authors were determined. Besides, the emerging of technologies in most of the research works conducted previously promote the hybridization of background of studies specifically in mathematics, biology, and computer science. The study is limited to English articles which was published by the Scopus database, ranging from the year of 1983 until 2023. The source is also limited to Scopus journals and proceedings only. As far as the authors are aware, this is the first study to address the splicing system topic from a bibliometric perspective. The authors believe that this bibliometric review will help scholars and researchers to stand firm bases regarding the scientific development of this field of study.

GrainGNN: A dynamic graph neural network for predicting 3D grain microstructure

We propose GrainGNN, a surrogate model for the evolution of polycrystalline grain structure under rapid solidification conditions in metal additive manufacturing. High fidelity simulations of solidification microstructures are typically performed using multicomponent partial differential equations (PDEs) with moving interfaces. The inherent randomness of the PDE initial conditions (grain seeds) necessitates ensemble simulations to predict microstructure statistics, e.g., grain size, aspect ratio, and crystallographic orientation. Currently such ensemble simulations are prohibitively expensive and surrogates are necessary.In GrainGNN, we use a dynamic graph to represent interface motion and topological changes due to grain coarsening. We use a reduced representation of the microstructure using hand-crafted features; we combine pattern finding and altering graph algorithms with two neural networks, a classifier (for topological changes) and a regressor (for interface motion). Both networks have an encoder-decoder architecture; the encoder has a multi-layer transformer long-short-term-memory architecture; the decoder is a single layer perceptron.We evaluate GrainGNN by comparing it to high-fidelity phase field simulations for in-distribution and out-of-distribution grain configurations for solidification under laser power bed fusion conditions. GrainGNN results in 80%–90% pointwise accuracy; and nearly identical distributions of scalar quantities of interest (QoI) between phase field and GrainGNN simulations compared using Kolmogorov-Smirnov test. GrainGNN's inference speedup (PyTorch on single x86 CPU) over a high-fidelity phase field simulation (CUDA on a single NVIDIA A100 GPU) is 150×–2000× for 100-initial grain problem. Further, using GrainGNN, we model the formation of 11,600 grains in 220 seconds on a single CPU core.

Structural origins of dielectric anomalies in the filled tetragonal tungsten bronze Sr2NaNb5O15

The tetragonal tungsten bronze, Sr2NaNb5O15, shows promise for application in high-temperature high-efficiency capacitors vital for the sustainable energy revolution. Previously, the structural complexity of this and related materials has obscured the mechanisms underpinning two large anomalies in relative permittivity (εr) which give rise to their exceptionally broad dielectric response. Here, we comprehensively investigate the structural evolution from −173 to 627 °C, combining electron, X-ray and neutron diffraction, electron microscopy, and first principles electronic structure calculations to unambiguously identify the structural origins of both anomalies. The peak in εr at 305 °C is associated with a polar-nonpolar phase transition, wherein cations displace along the c axis. Guided by DFT, we identify a further transition upon cooling, associated with the second peak at −14 °C, linked to the softening of an in-plane polar distortion with a correlation length limited by ferroelastic nano-domains arising from rigid-unit-like tilting of NbO6 octahedra at high temperature, imparting relaxor-like behaviour. Thus, the two dielectric anomalies in Sr2NaNb5O15 are associated with two distinct crystallographic phase transitions and their interplay with a microstructure that arises from a third, non-polar structural distortion. Chemical control of these will enable development of tuneable materials with dielectric properties suitable for high-temperature energy storage applications.

Cenozoic structure of the Zhu 3 Depression in the Pearl River Mouth Basin and its response to the dynamic background of the South China Sea

The Zhu 3 Depression is located at the transition between the South China Sea and the South China Block. The Cenozoic structure reflects the dynamic background of the South China Sea. We used 3D seismic and log data to study the structural evolution of the Zhu 3 Depression. We defined the characteristics of Cenozoic rift deformation and the migration of the depocentre based on fault activity and the distribution of sediment thickness. The spatial and temporal differences in the Cenozoic structure of the Zhu 3 Depression are due to the influence of pre-existing faults and regional stresses. Our results show that there are three populations of faults in the Zhu 3 Depression, striking NE, east–west and NW. The NE-striking faults are mainly large-scale boundary faults. The east–west-striking faults are small and were activated in the later stages of deformation. The NW-striking faults are continuous at depth, but are en echelon and parallel to each other at shallow depths. Based on these results, we suggest that the NE- and NW-striking pre-existing faults divide the Zhu 3 Depression into different structural zones and controlled the differences in deformation in the basin. The regional stress direction, which is controlled by regional plate interactions and the Red River Fault Zone, changed clockwise from NW-trending during the Paleocene to NE-trending during the Mid-Miocene. These findings will contribute to a better understanding of the evolution of the entire South China Sea. Thematic collection: This article is part of the Emerging knowledge on the tectonics of the South China Sea collection available at: https://www.lyellcollection.org/topic/collections/south-china-sea

Families of Stress–Strain, Relaxation and Creep Curves Generated by a Nonlinear Model for Thixotropic Viscoelastic-Plastic Media Accounting for Structure Evolution Part 2. Relaxation and Stress-Strain Curves

Families of Stress–Strain, Relaxation and Creep Curves Generated by a Nonlinear Model for Thixotropic Viscoelastic-Plastic Media Accounting for Structure Evolution Part 2. Relaxation and Stress-Strain Curves

Structural evolution and electronic properties of medium-sized boron clusters doped with selenium

The exploration of boron-doped clusters' structures and properties significantly advances our understanding of nanomaterials at the microscopic level. This study employs density functional theory to systematically investigate the structural evolution and electronic properties of singly Se-doped boron-based clusters, SeBn− (n = 16–24). The dopant atom exhibits a distinct preference for positioning outside the Bn−/0 framework, mirroring the arrangement found in the corresponding pure boron skeleton. Predicting the structural and electronic properties of doped clusters using simulated photoelectron spectra. Notably, magic clusters SeB19− and SeB23− are identified, showcasing remarkable relative stability. Furthermore, SeB24− is suggested to potentially exist as a pseudo-tubular isomer, representing a unique three-dimensional structure. The natural population analysis uncovers an electron transfer from Se to B atoms. The electronic localization function highlights substantial electron delocalization in SeBn−. Additionally, isochemical shielding surface analysis reveals pronounced aromaticity in the pseudo-tubular SeB24− isomer, thereby significantly enhancing the overall stability of the clusters.

On the structural evolution of pristine P2-type Na0.67Ni0.33Mn0.67O2 for symmetric full cell application

P2 type Na0.67Ni0.33Mn0.67O2 (NNMO) is a widely studied layered oxide cathode material for sodium-ion batteries (SIBs) because of its high capacity (160 mAhg-1 practically achieved) and broad voltage window (2–4.5 V). The redox activity in NNMO is shown by both Ni2+ and Mn4+ ions, making it a prospective symmetric SIB electrode material. The average working potential of the symmetric full cell is less due to the limited average working voltages of both the redoxes in a half cell between 2 V and 4.5 V, resulting in poor energy density. Herein, we report the feasibility of the NNMO symmetric full cell by widening the operational voltage window of NNMO. The electrochemical performance of NNMO half cells between 0.01 V and 4 V and the structural evolution during cycling are mapped by ex-situ XRD. Na0.44MnO2-like tunnel-type structure (Pbam) with high Na+ content (>0.90) exists at potentials close to the Mn3+/4+ redox reaction during cycling. The phase change was relatively reversible, implying that the NNMO anode works at such low voltages without the hazard of severe capacity losses. The symmetric full cell made using NNMO cycled between 0.01 V and 3 V and, at C/10 rate, delivered a capacity of ∼68 mAhg−1.

Evolution of interfacial nanostructures with temperature governing fretting wear in diamond-like carbon films

Diamond-like carbon (DLC) films are capable of offering low friction coefficient and high wear resistance when rubbed in both dry and lubricated interfaces. However, the inherent mechanisms governing fretting wear in DLC films with temperature are still not well comprehended. Herein, atomic-scale analysis was conducted to unveil the relationship between interfacial tribofilms and the fretting wear behaviors. The results emphasize the determining role of the interaction between the tribo-sintered tribofilms and the transferred carbon tribofilms, as well as the structural evolution in the DLC film with temperature. The room temperature (RT) fretting experiment establishes a bilayer nanostructured tribofilm with a C-rich transfer layer on a Fe-rich tribo-sintered layer. As the fretting temperature elevates the graphitization degree of the tribofilms exacerbates, surface oxidation and hydrogen effusion arise in the DLC film, resulting in higher friction coefficients and wear rates. Chromium outward diffusion at 500 °C establishes a Cr-rich interlayer in the tribofilm, which forms interfacial chromium-carbon bonds, promotes adhesive carbon transfer, and leads to the sharp increase of the friction force and wear rate. These findings provide new insights into the fretting wear mechanisms, and provide guidance for the application of DLC films in elevated-temperature fretting scenarios such as aero-engines tenon and spline connections.

Cross-scale deciphering thermal failure process of Ni-rich layered cathode

Ni-rich LiNixCoyMn1-x-yO2 (NCM) layered oxides are low-cost high-energy density cathode materials, but plagued by its poor thermal stability incurred safety concerns. The thermal failure process of the layered cathode is accompanied by heat generation and oxygen release, which drives the battery into thermal runaway (TR). Aiming to fully understand the TR process and the structure evolution, this work applies diverse characterization techniques onto a polycrystalline Ni-rich layered cathode (LiNi0.83Mn0.05Co0.12O2 (PCN83)) to comprehensively investigate its thermal failure process at multiple scales. From macro level, we validate that it is the cathode thermal failure that drives the battery from the heat accumulation stage into TR in adiabatic conditions. From micro level, transmission electron microscopy (TEM) verifies that the thermal failure of PCN83 starts from 150 °C, which is much lower than the TR temperature measured from macro level tests. We reveal that the PCN83 cathode experiences sequential phase transitions before the TR, where the phase transition mechanism is illustrated from the atomic scale and the pore evolution process is unraveled. In situ heating TEM further reveals that thermal failure is preferentially initiated from grain boundaries and defect regions. These findings provide an in-depth understanding of the whole thermal failure process of NMC-based layered cathode materials and sheds new lights on the rational design of Ni-rich cathode materials with improved thermal safety.