Revealing the Dynamic Lithiation Process of Copper Disulfide by in Situ TEM.

Transition metal oxides, fluorides, and sulfides are extensively studied as candidate electrode materials for lithium-ion batteries driven by the urgency of developing next-generation higher energy density lithium batteries. These conversion-type electrode materials often require nanosized active materials to enable a "smooth" lithiation and de-lithiation process during charge/discharge cycles, determined by their size, structure, and phase. Herein, the structural and chemical changes of Copper Disulfide (CuS2 ) hollow nanoparticles during the lithiation process through an in situ transmission electron microscopy (TEM) method are investigated. The study finds the hollow structure of CuS2 facilitates the quick formation of fluidic Li2 S "drops," accompanied by a de-sulfurization to the Cu7 S4 phase. Meanwhile, the metallic Cu phase emerges as fine nanoparticles and grows into nano-strips, which are embedded in the Li2 S/Cu7 S4 matrix. These complex nanostructured phases and their spatial distribution can lead to a low de-lithiation barrier, enabling fast reaction kinetics.

Deciphering the Metal-Support Interaction of Au/ZnO Catalyst Induced by H2 and O2 Pretreatment.

Metal-support interaction (MSI) provides great possibilities to tune the activity, selectivity, and stability of heterogeneous catalysts. Herein, the Au/ZnO catalyst is prepared by commercial ZnO and chloroauric acid, and the structure evolution of the catalyst pretreated by H2 and O2 gas at varied temperature is investigated to provide mechanistic insights of MSI. It is found that the H2 treatment at 300 °C and above can induce the formation of both the ZnOx overlayer and bulk Au-Zn alloy. In contrast, the O2 treatment can form the ZnOx overlayer at 500 °C and above without the formation of Au-Zn alloy. It is also revealed that the ZnOx overlayer is dynamically stable (permeable), which can provide access for reactant molecules during the reaction process. And, the Au-Zn alloy can recover to Au and ZnO under the CO oxidation reaction condition, which can be deemed as a re-activation process that endows H2 -treated samples with the superior activity and stability.

Oxygen-Loss-Induced Structural Degradation in ε-LiVOPO4.

The ε-LiVOPO4 cathode for Li-ion batteries has attracted wide attention with its multivalent electronic states and improved discharge capacity of over 300 mAh/g. Oxygen loss stands as a potential cause for structural degradations of the ε-LiVOPO4 cathode and its derivatives but has been barely studied. Through in situ environmental transmission electron microscopy, we probe lattice oxygen loss and the associated structural degradations by spatially and temporally resolving the atomic-scale structural dynamics and phase transformation pathways in ε-LiVOPO4. We demonstrate that the mild oxygen loss at 400 °C induces a topotactic phase transformation of ε-LiVOPO4 → α-Li3V2(PO4)3 in the particle surface via a nucleation and growth mechanism, leading to the formation of a core-shell configuration. The phase transformation can be reversed by switching to an oxidizing environment, in which the α-Li3V2(PO4)3 is reoxidized to ε-LiVOPO4. By contrast, oxygen loss at higher temperatures of 500 and 600 °C results in a high concentration of oxygen vacancies that subsequently induces irreversible structural damages including lattice amorphization and formation of nanocavities. This work illustrates the fundamental mechanisms governing the structural failure of oxide cathodes and underlines possible strategies to overcome such issues by exploiting environmental constraints.

Metal Affinity of Support Dictates Sintering of Gold Catalysts.

Sintering during heterogeneous catalytic reactions is one of the most notorious deactivation channels in catalysts of supported metal nanoparticles. It is therefore critical to understand the effect of support on the sintering behavior. Here, by using in situ aberration-corrected transmission electron microscopy and computational modeling, the atomic-scale dynamic interactions are revealed between Au nanoparticles and various supports. It is found that Au nanoparticles on ceria have a smaller contact angle and are apparently less mobile, especially at surface steps when compared with those on the amorphous silica. Analogous to hydrophilicity, we attribute the origin of mobility of small nanoparticles to metal affinity, which determines the interaction between metal and support material. Ab initio molecular dynamics (AIMD) and machine learning-based deep potential molecular dynamics (DPMD) simulations directly capture a coalescence process on the silica surface and the strong pinning of gold on ceria. The joint experimental and theoretical results on the atomic scale demonstrate the metal affinity of active and inert supports as the key descriptor pertinent to sintering and deactivation of heterogeneous catalysts.

Probing the Phase Transition during the Formation of Lithium Lanthanum Zirconium Oxide Solid Electrolyte.

Lithium lanthanum zirconium oxide (LLZO) has long been considered as a promising solid electrolyte for all-solid-state lithium (Li) metal batteries because of its interfacial stability when coupled with a Li metal anode. However, the cubic phase of LLZO (c-LLZO) with a higher Li-ion conductivity has a complex atomic structure and is subject to complicated phase transition during its processing and working conditions, which remain largely elusive. Here, we reveal the phase transition process during the formation of c-LLZO nanotubes through detailed microscopic characterization by scanning and transmission electron microscopy as well as X-ray diffraction. We find four typical stages during the formation of c-LLZO along with several intermediate phases including lanthanum (La)-rich cubic lanthanum zirconium oxide (La-rich c-LZO), c-LZO, and La-rich c-LLZO. We also reveal the role of m-Li2CO3 and h-Li2O2 as the "phase mediator".

In Situ Structural Dynamics of Atomic Defects in Tungsten Oxide.

Atomic defects are critical to tuning the physical and chemical properties of functional materials such as catalysts, semiconductors, and 2D materials. However, direct structural characterization of atomic defects, especially their formation and annihilation under practical conditions, is challenging yet crucial to understanding the underlying mechanisms driving defect dynamics, which remain mostly elusive. Here, through in situ atomic imaging by an aberration-corrected environmental transmission electron microscope (AC-ETEM), we directly visualize the formation and annihilation mechanism of planar defects in monoclinic WO3 on the atomic scale in real time. We captured the atomistic process of the nucleation dynamics of the dislocation core in the [010] direction, followed by its propagation to form a planar defect. Corroborated by density functional theory-based calculations, we rationalize the formation of dislocation through O extraction from bridge sites followed by an atomic channeling process. These in situ observations shed light on the defect dynamics in oxides and provide atomic insights into forming and manipulating defects in functional materials.

Revealing synergetic structural activation of a CuAu surface during water-gas shift reaction.

Bimetallic alloy catalysts show strong structural and compositional dependence on their activity, selectivity, and stability. Often referred to as the "synergetic effect" of two metal elements in the alloys, their detailed dynamic information, structurally and chemically, of catalyst surface under reaction conditions remains largely elusive. Here, using aberration-corrected environmental transmission electron microscopy, we visualize the atomic-scale synergetic surface activation of CuAu under a water­gas shift reaction condition. The unique "periodic" structural activation largely determines the dominating reaction pathway, which is related to a possible "carboxyl" reaction route corroborated by density functional theory­based calculation and ab initio molecular dynamics simulation. These results demonstrate how the alloy surface is activated and catalyzes the chemical reaction, which provides insights into catalyst design with atom precision.

A comparative study of oxide-derived Cu electrocatalysts through electrochemical vs. thermal reduction.

Herein, we demonstrated how the processing routes of OD-Cu affected the surface structure and electrochemical reduction of CO2. We found that the OD-Cu obtained by H2 annealing is large Cu nanoparticles (>100 nm) while the OD-Cu processed by electrochemical reduction possesses a porous structure of aggregated small Cu + Cu2O nanoparticles (∼5 nm). These structural differences lead to a distinct performance.

Atomic Defect Mediated Li-Ion Diffusion in a Lithium Lanthanum Titanate Solid-State Electrolyte.

Lithium lanthanum titanium oxide (LLTO) as a fast Li-ion conductor is a promising candidate for future all-solid-state Li batteries. Fundamental understanding of the microstructure of LLTO and its effect on the Li+ diffusion mechanism, especially across different length scales and interfaces, is a prerequisite to improving the material design and processing development of oxide-based solid electrolytes. Herein, through detailed structural analysis of LLTO ceramic pellets by aberration-corrected transmission electron microscopy, we discovered previously unreported intrinsic planar defects in LLTO single-crystal grains. These planar defects feature an antiphase boundary along specific crystal planes with a "rock-salt" structure enriched by Li within a few atomic layers. Corroborated by density-functional-theory-based calculations, we show an increased diffusion barrier across these planar defects inevitably lowers the bulk Li+ diffusivity of the oxide electrolyte.

Balancing the film strain of organic semiconductors for ultrastable organic transistors with a five-year lifetime.

The instability of organic field-effect transistors (OFETs) is one key obstacle to practical application and is closely related to the unstable aggregate state of organic semiconductors (OSCs). However, the underlying reason for this instability remains unclear, and no effective solution has been developed. Herein, we find that the intrinsic tensile and compressive strains that exist in OSC films are the key origins for aggregate state instability and device degradation. We further report a strain balance strategy to stabilize the aggregate state by regulating film thickness, which is based on the unique transition from tensile strain to compressive strain with increasing film thickness. Consequently, a strain-free and ultrastable OSC film is obtained by regulating the film thickness, with which an ultrastable OFET with a five-year lifetime is realized. This work provides a deeper understanding of and a solution to the instability of OFETs and sheds light on their industrialization.

Enhancing Li-ion conduction in composite polymer electrolytes using Li0.33La0.56TiO3 nanotubes.

Here, a poly(vinylidene fluoride) (PVDF)-based composite polymer electrolyte (CPE) with a unique Li0.33La0.56TiO3 (LLTO) nanotube filler, which shows a high Li-ion conductivity, is reported. Compared with LLTO nanoparticles (NPs) and nanowires (NWs), the LLTO nanotube fillers increase the interfacial area between PVDF and the LLTO filler, leading to the simple transportation of Li-ions through these interfacial pathways. In addition, the Li plating and stripping cycling performance of the CPEs is improved to 205 h at 0.1 mA cm-2, and the performance of the Li|CPEs|LiFePO4 cells also achieves a discharge capacity of 120 mA h g-1 after 100 cycles at 0.5C at room temperature. These results demonstrate an effective interfacial strategy for the design of high Li-ion conduction CPEs for all solid-state batteries.

Structural Evolution of Cu/ZnO Catalysts during Water-Gas Shift Reaction: An In Situ Transmission Electron Microscopy Study.

Supported metal catalysts experience significant structural evolution during the activation process and reaction conditions, which is critical to achieve a desired active surface and interface enabling efficient catalytic processes. However, such dynamic structural information and related mechanistic understandings remain largely elusive owing to the limitation of real-time capturing dynamic information under reaction conditions. Here, using in situ environment transmission electron microscopy, we demonstrate the atomic-scale structural evolution of the model Cu/ZnO catalyst under relevant water-gas shift reaction (WGSR) conditions. Under a CO gas environment, Cu nanoparticles decompose into smaller Cu species and redistribute on ZnO supports with either the crystalline Cu2O or amorphous CuOx phase due to a strong CO-Cu interaction. In addition, we visualize various metal-support interactions between Cu and ZnO under reaction conditions, e.g., ZnO clusters precipitating on Cu nanoparticles, which are critical to understand active sites of Cu/ZnO as catalysts for WGSR. These in situ atomic-scale observations highlight the dynamic interplays between Cu and ZnO that can be extended to other supported metal catalysts.

Atomic-Scale Interfacial Phase Transformation Governed Cu Oxidation in Water Vapor.

Metal oxidation initiates from surface adsorption to subsurface and bulk reaction through continuous interfacial phase transformation from metals to oxides. How the initial interfacial process affects the whole process of metal oxidation remains largely elusive because of the lack of direct observation of the evolving interface. Here, through in situ atomic-scale environmental TEM observations of Cu surface reaction in water vapor, we demonstrate that the interfacial strain between the substrate and growing oxide is coupled into the continuing chemical reaction that determines the reaction kinetics. Atomic imaging of the reaction process in real time reveals that the growing oxides could temporarily possess a disordered CuOx phase to lower its interfacial strain with Cu substrate and can transform to a crystalline Cu2O phase later. This flexibility of the oxide phase results from the strong chemomechanical coupling during the interfacial phase transformation, which enhances the oxide penetration into the metal under water vapor.

Defect-driven selective metal oxidation at atomic scale.

Nanoscale materials modified by crystal defects exhibit significantly different behaviours upon chemical reactions such as oxidation, catalysis, lithiation and epitaxial growth. However, unveiling the exact defect-controlled reaction dynamics (e.g. oxidation) at atomic scale remains a challenge for applications. Here, using in situ high-resolution transmission electron microscopy and first-principles calculations, we reveal the dynamics of a general site-selective oxidation behaviour in nanotwinned silver and palladium driven by individual stacking-faults and twin boundaries. The coherent planar defects crossing the surface exhibit the highest oxygen binding energies, leading to preferential nucleation of oxides at these intersections. Planar-fault mediated diffusion of oxygen atoms is shown to catalyse subsequent layer-by-layer inward oxide growth via atomic steps migrating on the oxide-metal interface. These findings provide an atomistic visualization of the complex reaction dynamics controlled by planar defects in metallic nanostructures, which could enable the modification of physiochemical performances in nanomaterials through defect engineering.

Atomic Scale Mechanisms of Multimode Oxide Growth on Nickel-Chromium Alloy: Direct In Situ Observation of the Initial Oxide Nucleation and Growth.

The initial growth mode of oxide on alloy plays a decisive role in the development of protective oxide scales on metals and alloys, which is critical for their functionality for high temperature applications. However, the atomistic mechanisms dictating that the oxide growth remain elusive due to the lack of direct in situ observation of the initial oxide nucleation and growth at atomic-scale. Herein, we employed environmental transmission electron microscopy and the first-principles calculations to elucidate the initial atomic process of nickel-chromium (Ni-Cr) alloy oxidation. We directly revealed three different oxide growth modes of initial NiO islands on Ni-Cr alloy upon oxidation by O2, which result in distinct crystallography and morphology. The multimode oxide growth leads to irregular-shaped oxides, which is shown to be sensitive to the local mass transport. This localization of oxide growth mode is also demonstrated by the identified vigorous competence in oxide growth and thus shown to be kinetically controlled. The concept exemplified here provides insights into the oxide formation and has significant implications in other material and chemical processes involving oxygen gas, such as corrosion, heterogeneous catalysis, and ionic conduction.

Direct Visualization of Atomic-Scale Graphene Growth on Cu through Environmental Transmission Electron Microscopy.

The functionalities of two-dimensional (2D) materials are solely determined by their perfect single-layer lattice or precisely stacking of multiple lattice planes, which is predominately determined during their growth process. Although the growth of graphene has been successfully achieved on different substrates with a large area up to millimeters, direct visualization of atomic-scale graphene growth in real time still lacks, which is vital to decipher atomistic mechanisms of graphene growth. Here, we employ aberration-corrected environmental transmission electron microscopy (AC-ETEM) to visualize the nucleation and growth of graphene at the atomic scale in real time. We find a unique lateral epitaxial growth process of graphene on Cu edges under the CO2 atmosphere with a ledge-flow process. The nucleation of graphene nuclei from amorphous carbon atoms also has been found to proceed with a gradual ordering of in-plane carbon atoms. The coalescence of smaller graphene nanoislands to form large ones is thermodynamically favored, and the evolution of atomic structures at grain boundaries is also revealed in great details. These atomic insights obtained from real-time observations can provide direct evidence for the growth mechanisms of graphene, which can be extended to other 2D materials.

Electrolyte-Phobic Surface for the Next-Generation Nanostructured Battery Electrodes.

Nanostructured electrodes are among the most important candidates for high-capacity battery chemistry. However, the high surface area they possess causes serious issues. First, it would decrease the Coulombic efficiencies. Second, they have significant intakes of liquid electrolytes, which reduce the energy density and increase the battery cost. Third, solid-electrolyte interphase growth is accelerated, affecting the cycling stability. Therefore, the interphase chemistry regarding electrolyte contact is crucial, which was rarely studied. Here, we present a completely new strategy of limiting effective surface area by introducing an "electrolyte-phobic surface". Using this method, the electrolyte intake was limited. The initial Coulombic efficiencies were increased up to ∼88%, compared to ∼60% of the control. The electrolyte-phobic layer of Si particles is also compatible with the binder, stabilizing the electrode for long-term cycling. This study advances the understanding of interphase chemistry, and the introduction of the universal concept of electrolyte-phobicity benefits the next-generation battery designs.

Atomic-Scale Dynamic Interaction of H_{2}O Molecules with Cu Surface.

Atomic-scale interaction of water vapor with metal surfaces beyond surface adsorption under technologically relevant conditions remains mostly unexplored. Using aberration-corrected environmental transmission electron microscopy, we reveal the dynamic surface activation of Cu by H_{2}O at elevated temperature and pressure. We find a structural transition from flat to corrugated surface for the Cu(011) under low water-vapor pressure. Increasing the water-vapor pressure leads to the surface reaction of Cu with dissociated H_{2}O, resulting in the formation of a metastable "bilayer" Cu─O─H phase. Corroborated by density functional theory and ab initio molecular dynamics calculations, the cooperative O and OH interaction with Cu is responsible for the formation and subsurface propagation of this phase.

Stress-resilient electrode materials for lithium-ion batteries: strategies and mechanisms.

Next-generation high-performance lithium-ion batteries (LIBs) with high energy and power density, long cycle life and uncompromising safety standards require new electrode materials beyond conventional intercalation compounds. However, these materials face a tradeoff between the high capacity and stable cycling because more Li stored in the materials also brings instability to the electrode. Stress-resilient electrode materials are the solution to balance this issue, where the decoupling of strong chemomechanical effects on battery cycling is a prerequisite. This review covers the (de)lithiation behaviors of the alloy and conversion-type anodes and their stress mitigation strategies. We highlight the reaction and degradation mechanisms down to the atomic scale revealed by in situ methods. We also discuss the implications of these mechanistic studies and comment on the effectiveness of the electrode structural and chemical designs that could potentially enable the commercialization of the next generation LIBs based on high-capacity anodes.

Atomic-scale phase separation induced clustering of solute atoms.

Dealloying typically occurs via the chemical dissolution of an alloy component through a corrosion process. In contrast, here we report an atomic-scale nonchemical dealloying process that results in the clustering of solute atoms. We show that the disparity in the adatom-substrate exchange barriers separate Cu adatoms from a Cu-Au mixture, leaving behind a fluid phase enriched with Au adatoms that subsequently aggregate into supported clusters. Using dynamic, atomic-scale electron microscopy observations and theoretical modeling, we delineate the atomic-scale mechanisms associated with the nucleation, rotation and amorphization-crystallization oscillations of the Au clusters. We expect broader applicability of the results because the phase separation process is dictated by the inherent asymmetric adatom-substrate exchange barriers for separating dissimilar atoms in multicomponent materials.