Recent Progress of In Situ Transmission Electron Microscopy for Energy Materials

In situ transmission electron microscopy (TEM) is one of the most powerful approaches for revealing physical and chemical process dynamics at atomic resolutions. The most recent developments for in situ TEM techniques are summarized; in particular, how they enable visualization of various events, measure properties, and solve problems in the field of energy by revealing detailed mechanisms at the nanoscale. Related applications include rechargeable batteries such as Li-ion, Na-ion, Li–O₂, Na–O₂, Li–S, etc., fuel cells, thermoelectrics, photovoltaics, and photocatalysis. To promote various applications, the methods of introducing the in situ stimuli of heating, cooling, electrical biasing, light illumination, and liquid and gas environments are discussed. The progress of recent in situ TEM in energy applications should inspire future research on new energy materials in diverse energy-related areas.     

Lithiation Mechanism of Tunnel‐Structured MnO2 Electrode Investigated by In Situ Transmission Electron Microscopy

Manganese oxide (α‐MnO₂) has been considered a promising energy material, including as a lithium‐based battery electrode candidate, due to its environmental friendliness. Thanks to its unique 1D [2 × 2] tunnel structure, α‐MnO₂ can be applied to a cathode by insertion reaction and to an anode by conversion reaction in corresponding voltage ranges, in a lithium‐based battery. Numerous reports have attributed its remarkable performance to its unique tunnel structure; however, the precise electrochemical reaction mechanism remains unknown. In this study, finding of the lithiation mechanism of α‐MnO₂ nanowire by in situ transmission electron microscopy (TEM) is reported. By elaborately modifying the existing in situ TEM experimental technique, rapid lithium‐ion diffusion through the tunnels is verified. Furthermore, by tracing the full lithiation procedure, the evolution of the MnO intermediate phase and the development of the MnO and Li₂O phases with preferred orientations is demonstrated, which explains how the conversion reaction occurs in α‐MnO₂ material. This study provides a comprehensive understanding of the electrochemical lithiation process and mechanism of α‐MnO₂ material, in addition to the introduction of an improved in situ TEM biasing technique.     

Analyzing Energy Materials by Cryogenic Electron Microscopy

Safe and high-energy-density rechargeable batteries are increasingly indispensable in the pursuit of a wireless and fossil-free society. Advancements in present battery technologies and the investigation of next-generation batteries highly depend on the ever-deepening fundamental understanding and the rational designs of working electrodes, electrolytes, and interfaces. However, accurately analyzing energy materials and interfaces is severely hindered by their intrinsic limitations of air and electron-beam sensitivity, which restrains the research of energy materials in a low-efficiency trial-and-error paradigm. The emergence of cryogenic electron microscopy (cryo-EM) has enabled the nondestructive characterization of air- and electron-beam sensitive energy materials in the microscale and nanoscale, and even at atomic resolutions, affording closer insights into the primary chemistry and physics of working batteries. Herein, the development of cryo-EM and the applications in detecting energy materials are reviewed and analyzed from its overwhelming advantages in disclosing the underlying mystery of energy materials. Critical sample preparation methods as the precondition for cryo-EM are compared, which strongly affect the characterization accuracy. Furthermore, new developments in the analysis of energy materials, especially bulk electrodes and interfaces in lithium metal batteries, are presented according to different functions of cryo-EM. Finally, future directions of cryo-EM for analyzing energy materials are prospected.     

Electron Diffraction Using Transmission Electron Microscopy

Electron diffraction via the transmission electron microscope is a powerful method for characterizing the structure of materials, including perfect crystals and defect structures. The advantages of electron diffraction over other methods, e.g., x-ray or neutron, arise from the extremely short wavelength (≈2 pm), the strong atomic scattering, and the ability to examine tiny volumes of matter (≈10 nm³). The NIST Materials Science and Engineering Laboratory has a history of discovery and characterization of new structures through electron diffraction, alone or in combination with other diffraction methods. This paper provides a survey of some of this work enabled through electron microscopy.     

Advanced Electron Microscopy for Advanced Materials

The idea of this Review is to introduce newly developed possibilities of advanced electron microscopy to the materials science community. Over the last decade, electron microscopy has evolved into a full analytical tool, able to provide atomic scale information on the position, nature, and even the valency atoms. This information is classically obtained in two dimensions (2D), but can now also be obtained in 3D. We show examples of applications in the field of nanoparticles and interfaces.     

Liquid‐Phase Transmission Electron Microscopy for Studying Colloidal Inorganic Nanoparticles

For the past few decades, nanoparticles of various sizes, shapes, and compositions have been synthesized and utilized in many different applications. However, due to a lack of analytical tools that can characterize structural changes at the nanoscale level, many of their growth and transformation processes are not yet well understood. The recently developed technique of liquid‐phase transmission electron microscopy (TEM) has gained much attention as a new tool to directly observe chemical reactions that occur in solution. Due to its high spatial and temporal resolution, this technique is widely employed to reveal fundamental mechanisms of nanoparticle growth and transformation. Here, the technical developments for liquid‐phase TEM together with their application to the study of solution‐phase nanoparticle chemistry are summarized. Two types of liquid cells that can be used in the high‐vacuum conditions required by TEM are discussed, followed by recent in situ TEM studies of chemical reactions of colloidal nanoparticles. New findings on the growth mechanism, transformation, and motion of nanoparticles are subsequently discussed in detail.     

New Developments in Transmission Electron Microscopy for Nanotechnology

High‐resolution transmission electron microscopy (HRTEM) is one of the most powerful tools used for characterizing nanomaterials, and it is indispensable for nanotechnology. This paper reviews some of the most recent developments in electron microscopy techniques for characterizing nanomaterials. The review covers the following areas: in‐situ microscopy for studying dynamic shape transformation of nanocrystals; in‐situ nanoscale property measurements on the mechanical, electrical and field emission properties of nanotubes/nanowires; environmental microscopy for direct observation of surface reactions; aberration‐free angstrom‐resolution imaging of light elements (such as oxygen and lithium); high‐angle annular‐dark‐field scanning transmission electron microscopy (STEM); imaging of atom clusters with atomic resolution chemical information; electron holography of magnetic materials; and high‐spatial resolution electron energy‐loss spectroscopy (EELS) for nanoscale electronic and chemical analysis. It is demonstrated that the picometer‐scale science provided by HRTEM is the foundation of nanometer‐scale technology.     

Materials and Structures for Stretchable Energy Storage and Conversion Devices

Stretchable energy storage and conversion devices (ESCDs) are attracting intensive attention due to their promising and potential applications in realistic consumer products, ranging from portable electronics, bio‐integrated devices, space satellites, and electric vehicles to buildings with arbitrarily shaped surfaces. Material synthesis and structural design are core in the development of highly stretchable supercapacitors, batteries, and solar cells for practical applications. This review provides a brief summary of research development on the stretchable ESCDs in the past decade, from structural design strategies to novel materials synthesis. The focuses are on the fundamental insights of mechanical characteristics of materials and structures on the performance of the stretchable ESCDs, as well as challenges for their practical applications. Finally, some of the important directions in the areas of material synthesis and structural design facing the stretchable ESCDs are discussed.     

Hollow Ptychography: Toward Simultaneous 4D Scanning Transmission Electron Microscopy and Electron Energy Loss Spectroscopy

With the recent development of high-acquisition-speed pixelated detectors, 4D scanning transmission electron microscopy (4D-STEM) is becoming routinely available in high-resolution electron microscopy. 4D-STEM acts as a “universal” method that provides local information on materials that is challenging to extract from bulk techniques. It extends conventional STEM imaging to include super-resolution techniques and to provide quantitative phase-based information, such as differential phase contrast, ptychography, or Bloch wave phase retrieval. However, an important missing factor is the chemical and bonding information provided by electron energy loss spectroscopy (EELS). 4D-STEM and EELS cannot currently be acquired simultaneously due to the overlapping geometry of the detectors. Here, the feasibility of modifying the detector geometry to overcome this challenge for bulk specimens is demonstrated, and the use of a partial or defective detector for ptycholgaphic structural imaging is explored. Results show that structural information beyond the diffraction-limit and chemical information from the material can be extracted together, resulting in simultaneous multi-modal measurements, adding the additional dimensions of spectral information to 4D datasets.     

Low Voltage Transmission Electron Microscopy of Graphene

The initial isolation of graphene in 2004 spawned massive interest in this two‐dimensional pure sp² carbon structure due to its incredible electrical, optical, mechanical, and thermal effects. This in turn led to the rapid development of various characterization tools for graphene. Examples include Raman spectroscopy and scanning tunneling microscopy. However, the one tool with the greatest prowess for characterizing and studying graphene is the transmission electron microscope. State‐of‐the‐art (scanning) transmission electron microscopes enable one to image graphene with atomic resolution, and also to conduct various other characterizations simultaneously. The advent of aberration correctors was timely in that it allowed transmission electron microscopes to operate with reduced acceleration voltages, so that damage to graphene is avoided while still providing atomic resolution. In this comprehensive review, a brief introduction is provided to the technical aspects of transmission electron microscopes relevant to graphene. The reader is then introduced to different specimen preparation techniques for graphene. The different characterization approaches in both transmission electron microscopy and scanning transmission electron microscopy are then discussed, along with the different aspects of electron diffraction and electron energy loss spectroscopy. The use of graphene for other electron microscopy approaches such as in‐situ investigations is also presented.     

扫描透射电镜中厚样品的电子散射与透过率特性的模拟研究

电子散射和电子透过率是影响厚膜样品扫描透射电镜成像及其检测应用的重要因素。本文根据样品材料中电子的弹性散射和非弹性散射模型,采用蒙特卡罗方法模拟了能量为100~300 keV的电子在微米级厚非晶薄膜样品中的散射过程,并计算了在扫描透射电镜明场模式下的电子透过率特性。电子透射厚样品的散射次数和出射角分布都由于样品厚度的增大而明显增大且展宽。所获得的电子透过率随样品厚度的变化规律与文献中实验报道一致。分析了入射电子能量、接收半张角及样品材料类型等参数对电子透过率的影响。结果表明电子透过率随着电子能量的提高而增大,随着样品材料的原子序数和密度的增大而减小。模拟结果还证实,部分电子经多重弹性散射而返回接收半张角会使电子透过率的减小偏离指数线性变化。     

Nanostructured Materials for Electrochemical Energy Conversion and Storage Devices

One of the greatest challenges for our society is providing powerful electrochemical energy conversion and storage devices. Rechargeable lithium‐ion batteries and fuel cells are amongst the most promising candidates in terms of energy densities and power densities. Nanostructured materials are currently of interest for such devices because of their high surface area, novel size effects, significantly enhanced kinetics, and so on. This Progress Report describes some recent developments in nanostructured anode and cathode materials for lithium‐ion batteries, addressing the benefits of nanometer‐size effects, the disadvantages of ‘nano’, and strategies to solve these issues such as nano/micro hierarchical structures and surface coatings, as well as developments in the discovery of nanostructured Pt‐based electrocatalysts for direct methanol fuel cells (DMFCs). Approaches to lowering the cost of Pt catalysts include the use of i) novel nanostructures of Pt, ii)new cost‐effective synthesis routes, iii) binary or multiple catalysts, and iv) new catalyst supports.

     

Writing Silica Structures in Liquid with Scanning Transmission Electron Microscopy

Silica nanoparticles are imaged in solution with scanning transmission electron microscopy (STEM) using a liquid cell with silicon nitride (SiN) membrane windows. The STEM images reveal that silica structures are deposited in well‐defined patches on the upper SiN membranes upon electron beam irradiation. The thickness of the deposits is linear with the applied electron dose. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) demonstrate that the deposited patches are a result of the merging of the original 20 nm‐diameter nanoparticles, and that the related surface roughness depends on the electron dose rate used. Using this approach, sub‐micrometer scale structures are written on the SiN in liquid by controlling the electron exposure as function of the lateral position.     

Probing Sodium Storage Mechanism in Hollow Carbon Nanospheres Using Liquid Phase Transmission Electron Microscopy

Carbonaceous materials are promising sodium-ion battery anodes. Improving their performance requires a detailed understanding of the ion transport in these materials, some important aspects of which are still under debate. In this work, nitrogen-doped porous hollow carbon spheres (N-PHCSs) are employed as a model system for operando analysis of sodium storage behavior in a commercial liquid electrolyte at the nanoscale. By combining the ex situ characterization at different states of charge with operando transmission electron microscopy experiments, it is found that a solvated ionic layer forms on the surface of N-PHCSs at the beginning of sodiation, followed by the irreversible shell expansion due to the solid-electrolyte interphase (SEI) formation and subsequent storage of Na(0) within the porous carbon shell. This shows that binding between Na(0) and C creates a Schottky junction making Na deposition inside the spheres more energetically favorable at low current densities. During sodiation, the SEI fills the gap between N-PHCSs, binding spheres together and facilitating the sodium ions' transport toward the current collector and subsequent plating underneath the electrode. The N-PHCSs layer acts as a protective layer between the electrolyte and the current collector, suppressing the possible growth of dendrites at the anode.     

Lattice Distortion Analysis Directly from High Resolution Transmission Electron Microscopy Images—the LADIA Program Package

Direct strain mapping from high resolution transmission electron microscopy images is possible for coherent structures.At proper imaging conditions the intensity peaks in the image have a constant spatial relationship with the projected atom columns.This allows the determination of the geometry of the projected unit cell without comparison with image simulations.The fast procedure is particularly suited for the analysis of large areas.The software package LADIA is written in the PV-WAVE code and provides all necessary tools for image processing and analysis.Image iintensity peaks are determined by a cross-correlation technique,which avoids problems from noise in the low spatial frequency renage.The lower limit of strain that can be detected at a sampling rate of 44 pixels/nm is ≈2%.     

Isotope Substitution Extends the Lifetime of Organic Molecules in Transmission Electron Microscopy

Structural characterisation of individual molecules by high‐resolution transmission electron microscopy (HRTEM) is fundamentally limited by the element and electron energy‐specific interactions of the material with the high energy electron beam. Here, the key mechanisms controlling the interactions between the e‐beam and C–H bonds, present in all organic molecules, are examined, and the low atomic weight of hydrogen—resulting in its facile atomic displacement by the e‐beam—is identified as the principal cause of the instability of individual organic molecules. It is demonstrated theoretically and proven experimentally that exchanging all hydrogen atoms within molecules with the deuterium isotope, and therefore doubling the atomic weight of the lightest atoms in the structure, leads to a more than two‐fold increase in the stability of organic molecules in the e‐beam. Substitution of H for D significantly reduces the amount of kinetic energy transferred from the e‐beam to the atom (main factor contributing to stability) and also increases the barrier for bond dissociation, primarily due to the changes in the zero‐point energy of the C–D vibration (minor factor). The extended lifetime of coronene‐d₁₂, used as a model molecule, enables more precise analysis of the inter‐molecular spacing and more accurate measurement of the molecular orientations.