In situ atomic-scale tracking of unusual interface reaction circulation and phase reversibility in(de)potassiated alloy-typed anode

Alloy-typed anode materials,endowed innately with high theoretical specific capacity,hold great promise as an alternative to intercalation-typed counterparts for alkali-ion batteries.Despite tremendous efforts devoted to addressing drastic volume change and severe pulverization issues of such anodes,the underlying mechanisms involving dynamic phase evolutions and reaction kinetics have not yet been fully comprehended.Herein,taking antimony(Sb)anode as a representative paradigm,its microscopic operating mechanisms down to the atomic scale during live(de)potassiation cycling are systematically unraveled using in situ transmission electron microscopy.Highly reversible phase transformations at single-particle level,that are Sb←→KSb_(2)←→KSb←→K_5Sb_(4)←→K_(3)Sb,were revealed during cycling.Meanwhile,multiple phase interfaces associated with different reaction kinetics coexisted and this phenomenon was properly elucidated in the context of density functional theory calculations.Impressively,previously unexplored unidirectional circulation of reaction interfaces within individual Sb particle is confirmed for both potassiation and depotassiation.Based on the empirical results,the surface diffusion-mediated potassiation-depotassiation pathways at single-particle level are suggested.This work affords new insights into energy storage mechanisms of Sb anode and valuable guidance for targeted optimization of alloy-typed anodes(not limited to Sb)toward advanced potassium-ion batteries.

In situ observation of the electrochemical behavior of Li–CO_(2)/O_(2)batteries in an environmental transmission electron microscope

Li–CO_(2)/O_(2)batteries,a promising energy storage technology,not only provide ultrahigh discharge capacity but also capture CO_(2)and turn it into renewable energy.Their electrochemical reaction pathways'ambiguity,however,creates a hurdle for their practical application.This study used copper selenide(CuSe)nanosheets as the air cathode medium in an environmental transmission electron microscope to in situ study Li–CO_(2)/O_(2)(mix CO_(2)as well as O_(2)at a volume ratio of 1:1)and Li–O_(2)batteries as well as Li–CO_(2)batteries.Primary discharge reactions take place successively in the Li–CO_(2)/O_(2)–CuSe nanobattery:(I)4Li^(+)+O_(2)+4e^(−)→2Li_(2)O;(II)Li_(2)O+CO_(2)→Li_(2)CO_(3).The charge reaction proceeded via(III)2Li_(2)CO_(3)→4Li^(+)+2CO_(2)+O_(2)+4e^(−).However,Li–O_(2)and Li–CO_(2)nanobatteries showed poor cycling stability,suggesting the difficulty in the direct decomposition of the discharge product.The fluctuations of the Li–CO_(2)/O_(2)battery's electrochemistry were also shown to depend heavily on O_(2).The CuSe‐based Li–CO_(2)/O_(2)battery showed exceptional electrochemical performance.The Li^–CO_(2)/O_(2)battery offered a discharge capacity apex of 15,492 mAh g^(−1) and stable cycling 60 times at 100 mA g^(−1).Our research offers crucial insight into the electrochemical behavior of Li–CO_(2)/O_(2),Li–O_(2),and Li–CO_(2)nanobatteries,which may help the creation of high‐performance Li–CO_(2)/O_(2)batteries for energy storage applications.

Rational design of diamond through microstructure engineering:From synthesis to applications

Diamond possesses excellent thermal conductivity and tunable bandgap.Currently,the high-pressure,high-temperature,and chemical vapor deposition methods are the most promising strategies for the commercial-scale production of synthetic diamond.Although diamond has been extensively employed in jewelry and cutting/grinding tasks,the realization of its high-end applications through microstructure engineering has long been sought.Herein,we discuss the microstructures encountered in diamond and further concentrate on cutting-edge investigations utilizing electron microscopy techniques to illuminate the transition mechanism between graphite and diamond during the synthesis and device constructions.The impacts of distinct microstructures on the electrical applications of diamond,especially the photoelectrical,electrical,and thermal properties,are elaborated.The recently reported elastic and plastic deformations revealed through in situ microscopy techniques are also summarized.Finally,the limitations,perspectives,and corresponding solutions are proposed.

A Study of Near-and Super-Critical Fluids Using Diamond Anvil Cell and in-Situ FT-IR Spectroscopy

The phase relation and solution structure of water and NaCl aqueous solution have been observed and examined by using the hydrothermal diamond anvil cell (HDAC) at elevated temperatures and pressures and the in situ FT-IR spectroscopy. The temperature of observations ranges from 25 to 850°C and the pressure up to 10 or 30 kb. At first, we observed the phase transition process from halite+liquid+vapour (H+L+V) to L+H, then to L (or supercritical fluid, SCF), and another path: H+L+V→L+V→L (or SCF) in heating process. By means of the visual microscope, the authors found that in the L+V immiscibility field L+V exhibits an ordered structure, i.e. a large visual cluster of solvent around ions. The liquid phase is manifested by vapour bubbles. When phase transitions are observed, the authors examined their infrared spectra by using the FT-IR microscopy simultaneously. In the case of the phase transition from liquid (L) to liquid + vapor (L+V) immisciblity field of NaCl solutions, a sudden change (strong frequency shift) of infrared spectra of the aqueous solution is observed near the critical temperature of water as the temperature is raised from 25 to 650°C. The frequency of the maximum intensity of OH symmetric and asymmetric vibration varies with respect to temperature. The sharp peak of the OH stretching vibration of the maximum intensity appears in an interval from 300 to 400°C. It is indicated that the hydrogen bonding network is weakened and broken at last near the critical point of water, which causes the aqueous solution to become more associated. Besides, a pressure indicator (a mineral or compound) was introduced to the HDAC.

Recent advances in the mechanics of 2D materials

The exceptional physical properties and unique layered structure of two-dimensional(2D)materials have made this class of materials great candidates for applications in electronics,energy conversion/storage devices,nanocomposites,and multifunctional coatings,among others.At the center of this application space,mechanical properties play a vital role in materials design,manufacturing,integration and performance.The emergence of 2D materials has also sparked broad scientific inquiry,with new understanding of mechanical interactions between 2D structures and interfaces being of great interest to the community.Building on the dramatic expansion of recent research activities,here we review significant advances in the understanding of the elastic properties,in-plane failures,fatigue performance,interfacial shear/friction,and adhesion behavior of 2D materials.In this article,special emphasis is placed on some new 2D materials,novel characterization techniques and computational methods,as well as insights into deformation and failure mechanisms.A deep understanding of the intrinsic and extrinsic factors that govern 2D material mechanics is further provided,in the hopes that the community may draw design strategies for structural and interfacial engineering of 2D material systems.We end this review article with a discussion of our perspective on the state of the field and outlook on areas for future research directions.

Interface catalytic reduction of alumina by nickle for the aluminum nanowire growth: Dynamics observed by in situ TEM

Metal nanowires show promise in a broad range of applications and can be fabricated via a number of methods,such as vapor–liquid–solid process and template-based electrodeposition.However,the synthesis of Al nanowires(NWs)is still challenging from the stable alumina substrate.In this work,the Ni-catalyzed fabrication of Al NWs has been realized using various Al_(2)O_(3) substrates.The growth dynamics of Al NWs on Ni/Al_(2)O_(3) was studied using in situ transmission electron microscopy(TEM).The effect of alumina structures,compositions,and growth temperature were investigated.The growth of Al NWs correlates with the Na addition to the alumina support.Since no eutectic mixture of nickel aluminide was formed,a mechanism of Ni-catalyzed reduction of Al_(2)O_(3) for Al NWs growth has been proposed instead of the vapor–liquid–solid mechanism.The key insights reported here are not restricted to Ni-catalyzed Al NWs growth but can be extended to understanding the dynamic change and catalytic performance of Ni/Al_(2)O_(3) under working conditions.

Structural and chemical transformations of CuZn alloy nanoparticles under reactive redox atmospheres:An in situ TEM study

Alloying metals to form intermetallics has been proven effective in tuning the chemical properties of metal-based catalysts.However,intermetallic alloys can undergo structural and chemical transformations under reactive conditions,leading to changes in their catalytic function.Elucidating and understanding these transformations are crucial for establishing relevant structureperformance relationships and for the rational design of alloy-based catalysts.In this work,we used CuZn alloy nanoparticles(NPs)as a model material system and employed in situ transmission electron microscopy(TEM)to investigate the structural and chemical changes of CuZn NPs under H_(2),O_(2)and their mixture.Our results show how CuZn NPs undergo sequential transformations in the gas mixture at elevated temperatures,starting with gradual leaching and segregation of Zn,followed by oxidation at the NP surface.The remaining copper at the core of particles can then engage in dynamic behavior,eventually freeing itself from the zinc oxide shell.The structural dynamics arises from an oscillatory phase transition between Cu and Cu_(2)O and is correlated with the catalytic water formation,as confirmed by in situ mass spectrometry(MS).Under pure H_(2)or O_(2)atmosphere,we observe different structural evolution pathways and final chemical states of CuZn NPs compared to those in the gas mixture.These results clearly demonstrate that the chemical state of alloy NPs can vary considerably under reactive redox atmospheres,particularly for those containing elements with distinct redox properties,necessitating the use of in situ or detailed ex situ characterizations to gain relevant insights into the states of intermetallic alloy-based catalysts and structure-activity relationships.

In Situ Electrochemical Transmission Electron Microscopy for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)possess promising application prospects for large-scale energy storage systems due to the abundance of sodium ions as a resource and their low cost.Development of advanced SIBs requires a clear understanding of the structures and kinetic/dynamic processes occurring in the cells during the charging/discharging process.In situ transmission electron microscopy(TEM)is a powerful tool for direct visualization of the phase transitions as well as morphological and structural evolutions of the electrodes during the electrochemical reaction process.Herein,we summarize the state-of-the-art in situ TEM studies on SIBs with a specific focus on real-time observations of the electrochemical behavior of battery materials.This review emphasizes the necessity of in situ TEM to elucidate fundamental issues regarding the reaction mechanism,phase transformation,structural evolution,and performance degradation of SIBs.Finally,critical challenges and emerging opportunities for in situ TEM research about SIBs are discussed.

Electrospun advanced nanomaterials for in situ transmission electron microscopy:Progress and perspectives

Electrospun nanofibers(NFs)have shown excellent properties including high porosity,abundant active sites,controllable diameter,uniform and designable structure,high mechanical strength,and superior resistance to external destruction,which are ideal nanoreactors for in situ characterizations.Among various techniques,in situ transmission electron microscopy(TEM)has enabled operando observation at the atomic level due to its high temporal and spatial resolution combined with excellent sensitivity,which is of great importance for rational materials design and performance improvement.In this review,the basic knowledge of in situ TEM techniques and the advantages of electrospun nanoreactors for in situ TEM characterization are first introduced.The recent development in electrospun nanoreactors for studying the physical properties,structural evolution,phase transition,and formation mechanisms of materials using in situ TEM is then summarized.The electrochemical behaviors of carbon nanofibers(CNFs),metal/metal oxide NFs,and solidelectrolyte interphase for different rechargeable batteries are highlighted.Finally,challenges faced by electrospun nanoreactors for in situ TEM characterization are discussed and potential solutions are proposed to advance this field.

In situ TEM visualization of Ag catalysis in Li-O_(2)nanobatteries

Lithium-oxygen(Li-O_(2))batteries have been considered as an ideal solution to solving the global energy crisis.Silver(Ag)and Agbased catalyst have been extensively studied due to their high catalytic activities in Li-O_(2)batteries.However,it remains a challenge to track the catalytic mechanism during the charge/discharge process.Here,a nanoscale processing method was used to assemble a Li-O_(2)nanobattery in an aberration-corrected environmental transmission electron microscope(ETEM),where a single Ag nanowire(NW)was used as catalyst for O_(2)electrode.A visualization of the lithium ion insertion process during the electrochemical reactions was achieved in this nanobattery.Numerous Ag nanoparticles(NPs)were observed on the surface of the Ag NW,which were covered by the discharge product Li2O_(2).By simultaneously studying the evolution of the interface and the phase transformation,it can be concluded that these Ag NPs wrapped around Ag NW acted as catalyst during the subsequent charge/discharge reaction.Based on these studies,Ag NPs decorated on porous carbon were synthesized,it can simultaneously improve the cycling stability(100 cycles)and the maximum specific capacity(17,371 mAh·g^(−1)at a current density of 100 mA·g^(−1))in a coin cell Li-O_(2)battery.This study suggests that nanoscale Ag may be a promising catalyst for Li-O_(2)battery.

Correlating the fluctuated growth of carbon nanotubes with catalyst evolution by atmospheric-pressure environmental transmission electron microscopy

Rate-controlled growth of carbon nanotubes(CNTs)and catalyst design are considered efficient ways for the preparation of CNTs with specific structures and properties.However,due to the difficulties in capturing the growth process of the CNTs with tiny size under a complex growth environment,the growth kinetics of CNTs and their correlation with the catalyst seed have been seldom revealed.Here,we investigated the growth process of CNTs from Ni nanoparticles(NPs)in real-time under atmospheric pressure using transmission electron microscopy equipped with a closed gas cell.It was found that the growth rates of CNTs fluctuated,and a phase transition from Ni_(3)C to Ni,and a reshaping of the catalyst NPs occurred during the growth process.We demonstrated that CNTs dynamically interacted with the connected catalyst NPs and the fluctuated growth rates of CNTs were correlated with the structure change of catalyst NPs.The origin of the growth rate fluctuation is attributed to the change of carbon concentration gradient in catalyst NPs.

Atomic-scale insights into the formation of 2D crystals from in situ transmission electron microscopy

Two-dimensional(2D)crystals are attractive due to their intriguing structures and properties which are strongly dependent on the synthesis conditions.To achieve their superior properties,it is of critical importance to fully understand the growth processes and mechanisms for tailored design and controlled growth of 2D crystals.Due to the high spatiotemporal resolution and the capability to mimic the realistic growth conditions,in situ transmission electron microscopy(TEM)becomes an effective way to monitor the growth process in real-time at the atomic scale,which is expected to provide atomic-scale insights into the nucleation and growth of 2D crystals.Here we review the recent in situ TEM works on the formation of 2D crystals under electron irradiation,thermal excitation as well as voltage bias.The underlying mechanisms are also elucidated in detail,providing key insights into the nucleation and formation of 2D crystals.

Unraveling the reaction mechanisms of electrode materials for sodiumion and potassium‐ion batteries by in situ transmission electron microscopy

Sodium ion batteries(SIBs)and potassium ion batteries(PIBs)have caught numerous attention due to the low cost and abundant availability of sodium and potassium.However,their power density,cycling stability and safety need further improvement for practical applications.Investigations on the reaction mechanisms and structural degradation when cycling are of great importance.In situ transmission electron microscopy(TEM)is one of the most significant techniques to understand and monitor electrochemical processes at an atomic scale with real-time imaging.In this review,the current progress in unraveling reaction mechanisms of electrode materials for SIBs and PIBs via in situ TEM is summarized.First,the importance of in situ TEM is highlighted.Then,based on the three types of electrochemical reaction,i.e.,intercalation reac-tion,conversion reaction and alloying reaction,the structural evolution and reaction kinetics at atomic resolution,and their relation to the electrochemical performance of electrode materials are reviewed and described in detail.Fi-nally,future directions of in situ TEM for SIBs and PIBs are proposed.Therefore,the in‐depth understanding revealed by in situ TEM will give an instructive guide in rational design of electrode materials for high performance electrode materials of SIBs and PIBs.

Hierarchical crystalline-amorphous nanocomposites with high strength and large deformability enabled by elemental diffusion

Amorphous/nanocrystalline dual-phase structures have recently emerged as an effective way for over-coming the strength-ductility trade-offand breaking the limitation of the reverse Hall-Petch effect.Here,we proposed a new strategy to develop a hierarchical and interconnected amorphous-crystalline nanocomposite arising from the nanoscale elemental interdiffusion and oxygen adsorption behavior dur-ing thermal treatment processes.The nanocomposite consisted of a three-dimensional(3D)hierarchical network structure where the crystalline phase(Cr-Co-Ni-Al)was embedded into the Al-O-based amor-phous phase network with critical feature sizes encompassing three orders of magnitude(from microm-eter to nanometer scale).It can achieve ultrahigh compression yield strength of-3.6 GPa with large homogeneous deformation of over 50%strain.The massive interstitial atoms induced lattice distortion and hierarchical amorphous phase boundary contributed to the strength improvement.in situ Uniaxial compression inside a transmission electron microscope(TEM)revealed that the exceptional deformability of the nanocomposites resulted from the homogenous plastic flow of nano-sized amorphous phase and the plastic co-deformation behavior restricted by the nano-architected dual-phase interface.The proposed dual-phase synthesis approach can outperform conventional nanolaminates design strategies in terms of the mechanical properties achievable while providing a pathway to easily tune the microstructure of these nanolaminates.

Visualizing the crystallization of sodium chloride under supersaturated condition

Crystallization in supersaturated solution plays a fundamental role in a variety of natural and industrial processes.However,a thorough understanding of crystallization phenomena in supersaturated solution is still difficult because the real-time visualization of crystallization processes under supersaturated condition is a great challenge.Herein,an electron beam-induced crystallization method was carried out in in situ liquid cell transmission electron microscopy(TEM)to visualize the crystallization of NaCl under supersaturated condition in real time.Crucial steps and behaviors in the crystallization of NaCl were captured and clarified,including the growth of NaCl nanocrystals with different morphologies,the formation of initial crystalline seeds from amorphous ion clusters,and the non-equilibrium growth behaviors caused by uneven distribution of precursor ions.This study provides the real-time visualization of detailed nucleation and growth behaviors in NaCl crystallization and brings an ideal strategy for investigating crystallization phenomena under supersaturated condition.

Structural evolution of Pt‐based oxygen reduction reaction electrocatalysts

The commercialization of proton exchange membrane fuel cells(PEMFCs)could provide a cleaner energy society in the near future.However,the sluggish reaction kinetics and harsh conditions of the oxygen reduction reaction affect the durability and cost of PEMFCs.Most previous reports on Pt-based electrocatalyst designs have focused more on improving their activity;however,with the commercialization of PEMFCs,durability has received increasing attention.In-depth insight into the structural evolution of Pt-based electrocatalysts throughout their lifecycle can contribute to further optimization of their activity and durability.The development of in situ electron microscopy and other in situ techniques has promoted the elucidation of the evolution mechanism.This mini review highlights recent advances in the structural evolution of Pt-based electrocatalysts.The mechanisms are adequately discussed,and some methods to inhibit or exploit the structural evolution of the catalysts are also briefly reviewed.

In Situ Imaging of Layer-by-Layer Sublimation of Suspended Graphene

An individual suspended graphene sheet was connected to a scanning tunneling microscopy probe inside a transmission electron microscope,and Joule heated to high temperatures.At high temperatures and under electron beam irradiation,the few-layer graphene sheets were removed layer-by-layer in the viewing area until a monolayer graphene was formed.The layer-by-layer peeling was initiated at vacancies in individual graphene layers.The vacancies expanded to form nanometer-sized holes,which then grew along the perimeter and propagated to both the top and bottom layers of a bilayer graphene joined by a bilayer edge.The layer-by-layer peeling was induced by atom sublimation caused by Joule heating and facilitated by atom displacement caused by high-energy electron irradiation,and may be harnessed to control the layer thickness of graphene for device applications.

In situ TEM observation of dissolution and regrowth dynamics of MoO2 nanowires under oxygen

Direct observation of the dissolution behavior of nanomaterials could provide fundamental insight to understanding their anisotropic properties and stability. The dissolution mechanism in solution and vacuum has been well documented. However, the gas-involved dissolution and regrowth have seldom been explored and the mechanisms remain elusive. We report herein, an in situ TEM study of the dissolution and regrowth dynamics of MoO2 nanowires under oxygen using environmental transmission electron microscopy （ETEM）. For the first time, oscillatory dissolution on the nanowire tip is revealed, and, intriguingly, simultaneous layer-by-layer regrowth on the sidewall facets is observed, leading to a shorter and wider nanowire. Combined with first-principles calculations, we found that electron beam irradiation caused oxygen loss in the tip facets, which resulted in changing the preferential growth facets and drove the morphology reshaping.

In situ observation of temperature-dependent atomistic and mesoscale oxidation mechanisms of aluminum nanoparticles

Oxidation is a universal process causing metals’corrosion and degradation.While intensive researches have been conducted for decades,the detailed atomistic and mesoscale mechanisms of metal oxidation are still not well understood.Here using in situ environmental transmission electron microscopy(E-TEM)with atomic resolution,we revealed systematically the oxidation mechanisms of aluminum from ambient temperature to^600℃.It was found that an amorphous oxide layer formed readily once Al was exposed to air at room temperature.At^150℃,triangle-shaped Al2O3 lamellas grew selectively on gas/solid(oxygen/amorphous oxide layer)interface,however,the thickness of the oxide layer slowly increased mainly due to the inward diffusion of oxygen.As the temperature further increased,partial amorphous-to-crystallization transition was observed on the amorphous oxide film,resulting in the formation of highly dense nano-cracks in the oxide layer.At^600℃,fast oxidation process was observed.Lamellas grew into terraces on the oxide/gas interface,indicating that the high temperature oxidation is controlled by the outward diffusion of Al.Single or double/multi-layers of oxide nucleated at the corners of the terraces,forming denseγ’-Al2O3,which is a metastable oxide structure but may be stabilized at nanoscale.

In-situ liquid-cell TEM study of radial flow-guided motion of octahedral Au nanoparticles and nanoparticle clusters

The dynamic behavior of octahedral gold nanopartides （NPs） and nanoparticle clusters （NPCs） in aqueous solution is studied by in-situ liquid-cell transmission electron microscopy （TEM）. The octahedral Au NPs/NPCs show preferential orientations in the liquid cell, due to the interaction with the SiNx window. The Au NPs show long-range reversible hopping and three-dimensional （3D） rotational motions in the liquid environment. At the same time, the Au NPCs and NPs perform slow stick-sUp and stick-roU motions, respectivel~ with a centripetal trend. The centripetal motions were explained by a liquid evaporation-induced radial flow model in which the NPCs/NPs trajectories are controlled by Stokes forces and surface friction by the silicon nitride window. The calculated radius-dependent force （Fc） on the NPCs/NPs shows a semi-linear correlation with the distance r between the NPCs/NPs and the center of mass, accompanied with stochastic fluctuations, in agreement with the model predictions. This work thus demonstrates the effectiveness of in situ liquid-cell TEM for the in-depth understanding of complicated liquid flow and force interactions in nanomaterials.