Amorphous Materials for Lithium-Ion and Post-Lithium-Ion Batteries.

Lithium-ion and post-lithium-ion batteries are important components for building sustainable energy systems. They usually consist of a cathode, an anode, an electrolyte, and a separator. Recently, the use of solid-state materials as electrolytes has received extensive attention. The solid-state electrolyte materials (as well as the electrode materials) have traditionally been overwhelmingly crystalline materials, but amorphous (disordered) materials are gradually emerging as important alternatives because they can increase the number of ion storage sites and diffusion channels, enhance solid-state ion diffusion, tolerate more severe volume changes, and improve reaction activity. To develop superior amorphous battery materials, researchers have conducted a variety of experiments and theoretical simulations. This review highlights the recent advances in using amorphous materials (AMs) for fabricating lithium-ion and post-lithium-ion batteries, focusing on the correlation between material structure and properties (e.g., electrochemical, mechanical, chemical, and thermal ones).  We  review both the conventional and the emerging characterization methods for analyzing AMs and present the roles of disorder in influencing the performances of various batteries such as those based on lithium, sodium, potassium, and zinc. Finally,  we  describe the challenges and perspectives for commercializing rechargeable AMs-based batteries.

New Emerging Fast Charging Microscale Electrode Materials.

Fast charging lithium (Li)-ion batteries are intensively pursued for next-generation energy storage devices, whose electrochemical performance is largely determined by their constituent electrode materials. While nanosizing of electrode materials enhances high-rate capability in academic research, it presents practical limitations like volumetric packing density and high synthetic cost. As an alternative to nanosizing, microscale electrode materials cannot only effectively overcome the limitations of the nanosizing strategy but also satisfy the requirement of fast-charging batteries. Therefore, this review summarizes the new emerging microscale electrode materials for fast charging from the commercialization perspective. First, the fundamental theory of electronic/ionic motion in both individual active particles and the whole electrode is proposed. Then, based on these theories, the corresponding optimization strategies are summarized toward fast-charging microscale electrode materials. In addition, advanced functional design to tackle the mechanical degradation problems related to next generation high capacity alloy- and conversion-type electrode materials (Li, S, Si et al.) for achieving fast charging and stable cycling batteries. Finally, general conclusions and the future perspective on the potential research directions of microscale electrode materials are proposed. It is anticipated that this review will provide the basic guidelines for both fundamental research and practical applications of fast-charging batteries.

True Meaning of Pseudocapacitors and Their Performance Metrics: Asymmetric versus Hybrid Supercapacitors.

The development of pseudocapacitive materials for energy-oriented applications has stimulated considerable interest in recent years due to their high energy-storing capacity with high power outputs. Nevertheless, the utilization of nanosized active materials in batteries leads to fast redox kinetics due to the improved surface area and short diffusion pathways, which shifts their electrochemical signatures from battery-like to the pseudocapacitive-like behavior. As a result, it becomes challenging to distinguish "pseudocapacitive" and "battery" materials. Such misconceptions have further impacted on the final device configurations. This Review is an earnest effort to clarify the confusion between the battery and pseudocapacitive materials by providing their true meanings and correct performance metrics. A method to distinguish battery-type and pseudocapacitive materials using the electrochemical signatures and quantitative kinetics analysis is outlined. Taking solid-state supercapacitors (SSCs, only polymer gel electrolytes) as an example, the distinction between asymmetric and hybrid supercapacitors is discussed. The state-of-the-art progress in the engineering of active materials is summarized, which will guide for the development of real-pseudocapacitive energy storage systems.

Methods for operando coherent X-ray diffraction of battery materials at the Advanced Photon Source.

Bragg coherent X-ray diffraction imaging has become valuable for visualization of the structural, morphological and strain evolution of crystals in operando electrode materials. As the electrode material particles (either in a single-crystal form or an aggregation form of single crystals) are evenly dispersed and randomly oriented in the electrode laminate, the submicrometer-sized coherentX-ray beam can be used to probe the local properties of electrode material crystals using two approaches. Coherent multi-crystal diffraction provides collective structural information of phase transitions in tens of crystals simultaneously as well as the individual behavior from single crystals, which are oriented at the Bragg condition in the X-ray illumination volume. Bragg coherent diffractive imaging enables one to monitor the evolution of the morphology and strain in individual crystals. This work explores and highlights the Bragg coherent X-ray diffraction measurements of battery electrode materials in operando conditions at the 34-ID-C beamline at the Advanced Photon Source. The experiment is demonstrated with NaNi1/3Fe1/3Mn1/3O2, a sodium-ion cathode material loaded in a half cell. The paper will discuss, in detail, the beamline setup, sample mounting and handling, alignment strategies and the data acquisition protocols.

Nanoscale Detection of Intermediate Solid Solutions in Equilibrated LixFePO4 Microcrystals.

Redox-driven phase transformations in solids determine the performance of lithium-ion batteries, crucial in the technological transition from fossil fuels. Couplings between chemistry and strain define reversibility and fatigue of an electrode. The accurate definition of all phases in the transformation, their energetics, and nanoscale location within a particle produces fundamental understanding of these couplings needed to design materials with ultimate performance. Here we demonstrate that scanning X-ray diffraction microscopy (SXDM) extends our ability to image battery processes in single particles. In LiFePO4 crystals equilibrated after delithiation, SXDM revealed the existence of domains of miscibility between LiFePO4 and Li0.6FePO4. These solid solutions are conventionally thought to be metastable, and were previously undetected by spectromicroscopy. The observation provides experimental verification of predictions that the LiFePO4-FePO4 phase diagram can be altered by coherency strain under certain interfacial orientations. It enriches our understanding of the interaction between diffusion, chemistry, and mechanics in solid state transformations.

Quantitative description on structure-property relationships of Li-ion battery materials for high-throughput computations.

Li-ion batteries are a key technology for addressing the global challenge of clean renewable energy and environment pollution. Their contemporary applications, for portable electronic devices, electric vehicles, and large-scale power grids, stimulate the development of high-performance battery materials with high energy density, high power, good safety, and long lifetime. High-throughput calculations provide a practical strategy to discover new battery materials and optimize currently known material performances. Most cathode materials screened by the previous high-throughput calculations cannot meet the requirement of practical applications because only capacity, voltage and volume change of bulk were considered. It is important to include more structure-property relationships, such as point defects, surface and interface, doping and metal-mixture and nanosize effects, in high-throughput calculations. In this review, we established quantitative description of structure-property relationships in Li-ion battery materials by the intrinsic bulk parameters, which can be applied in future high-throughput calculations to screen Li-ion battery materials. Based on these parameterized structure-property relationships, a possible high-throughput computational screening flow path is proposed to obtain high-performance battery materials.

Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in LixFePO4.

The performance of battery electrode materials is strongly affected by inefficiencies in utilization kinetics and cycle life as well as size effects. Observations of phase transformations in these materials with high chemical and spatial resolution can elucidate the relationship between chemical processes and mechanical degradation. Soft X-ray ptychographic microscopy combined with X-ray absorption spectroscopy and electron microscopy creates a powerful suite of tools that we use to assess the chemical and morphological changes in lithium iron phosphate (LiFePO4) micro- and nanocrystals that occur upon delithiation. All sizes of partly delithiated crystals were found to contain two phases with a complex correlation between crystallographic orientation and phase distribution. However, the lattice mismatch between LiFePO4 and FePO4 led to severe fracturing on microcrystals, whereas no mechanical damage was observed in nanoplates, indicating that mechanics are a principal driver in the outstanding electrode performance of LiFePO4 nanoparticles. These results demonstrate the importance of engineering the active electrode material in next generation electrical energy storage systems, which will achieve theoretical limits of energy density and extended stability. This work establishes soft X-ray ptychographic chemical imaging as an essential tool to build comprehensive relationships between mechanics and chemistry that guide this engineering design.

Crystal Structure Complexity and Approximate Limits of Possible Crystal Structures Based on Symmetry-Normalized Volumes.

Rules that control the arrangement of chemical species within crystalline arrays of different symmetry and structural complexity are of fundamental importance in geoscience, material science, physics, and chemistry. Here, the volume of crystal phases is normalized by their ionic volume and an algebraic index that is based on their space-group and crystal site symmetries. In correlation with the number of chemical formula units Z, the normalized volumes exhibit upper and lower limits of possible structures. A bottleneck of narrowing limits occurs for Z around 80 to 100, but the field of allowed crystalline configurations widens above 100 due to a change in the slope of the lower limit. For small Z, the highest count of structures is closer to the upper limit, but at large Z, most materials assume structures close to the lower limit. In particular, for large Z, the normalized volume provides rather narrow constraints for the prediction of novel crystalline phases. In addition, an index of higher and lower complexity of crystalline phases is derived from the normalized volume and tested against key criteria.

Polysulfides in Magnesium-Sulfur Batteries.

Mg-S batteries hold great promise as a potential alternative to Li-based technologies. Their further development hinges on solving a few key challenges, including the lower capacity and poorer cycling performance when compared to Li counterparts. At the heart of the issues is the lack of knowledge on polysulfide chemical behaviors in the Mg-S battery environment. In this Review, a comprehensive overview of the current understanding of polysulfide behaviors in Mg-S batteries is provided. First, a systematic summary of experimental and computational techniques for polysulfide characterization is provided. Next, conversion pathways for Mg polysulfide species within the battery environment are discussed, highlighting the important role of polysulfide solubility in determining reaction kinetics and overall battery performance. The focus then shifts to the negative effects of polysulfide shuttling on Mg-S batteries. The authors outline various strategies for achieving an optimal balance between polysulfide solubility and shuttling, including the use of electrolyte additives, polysulfide-trapping materials, and dual-functional catalysts. Based on the current understanding, the directions for further advancing knowledge of Mg polysulfide chemistry are identified, emphasizing the integration of experiment with computation as a powerful approach to accelerate the development of Mg-S battery technology.

Side Reactions/Changes in Lithium-Ion Batteries: Mechanisms and Strategies for Creating Safer and Better Batteries.

Lithium-ion batteries (LIBs), in which lithium ions function as charge carriers, are considered the most competitive energy storage devices due to their high energy and power density. However, battery materials, especially with high capacity undergo side reactions and changes that result in capacity decay and safety issues. A deep understanding of the reactions that cause changes in the battery's internal components and the mechanisms of those reactions is needed to build safer and better batteries. This review focuses on the processes of battery failures, with voltage and temperature as the underlying factors. Voltage-induced failures result from anode interfacial reactions, current collector corrosion, cathode interfacial reactions, overcharge, and over-discharge, while temperature-induced failure mechanisms include SEI decomposition, separator damage, and interfacial reactions between electrodes and electrolytes. The review also presents protective strategies for controlling these reactions. As a result, the reader is offered a comprehensive overview of the safety features and failure mechanisms of various LIB components.

Pathways to Next-Generation Fire-Safe Alkali-Ion Batteries.

High energy and power density alkali-ion (i.e., Li+ , Na+ , and K+ ) batteries (AIBs), especially lithium-ion batteries (LIBs), are being ubiquitously used for both large- and small-scale energy storage, and powering electric vehicles and electronics. However, the increasing LIB-triggered fires due to thermal runaways have continued to cause significant injuries and casualties as well as enormous economic losses. For this reason, to date, great efforts have been made to create reliable fire-safe AIBs through advanced materials design, thermal management, and fire safety characterization. In this review, the recent progress is highlighted in the battery design for better thermal stability and electrochemical performance, and state-of-the-art fire safety evaluation methods. The key challenges are also presented associated with the existing materials design, thermal management, and fire safety evaluation of AIBs. Future research opportunities are also proposed for the creation of next-generation fire-safe batteries to ensure their reliability in practical applications.

Nanostructured Porous Polymer with Low Volume Expansion, Structural Distortion, and Gradual Activation for High and Durable Lithium Storage.

Organic compounds exhibit great potential as sustainable, tailorable, and environmentally friendly electrode materials for rechargeable batteries. However, the intrinsic defects of organic electrodes, including solubility, low ionic conductivity, and restricted electroactivity sites, will inevitably decrease the cycling life and capacity. We herein designed and prepared nanostructured porous polymers (NPP) with a simple one-pot method to overcome the above defects. Theoretical calculations and experimental results demonstrate that the as-synthesized NPP exhibited low volume expansion, molecular-structural distortion, and a gradual function activation process during cycling, thus exhibiting superior, high, and durable lithium storage. The gradual molecular distortion during the lithium storage processes provides more redox-active sites for Li storage, increasing the Li-storage capacity. Ex situ spectrum studies reveal the redox reaction mechanism of Li storage and demonstrate a gradual activation process during the repeated charging/discharging until the full storage of 18 Li ions is achieved. Additionally, a real-time observation on the NPP anode by in situ transmission electron microscope reveals a slight volume expansion during the repeating lithiation and delithiation processes, ensuring its structural integrity during cycling. This quantitative work for high-durability lithium storage could be of immediate benefit for designing organic electrode materials.

Towards the Future of Polymeric Hybrids of Two-Dimensional Black Phosphorus or Phosphorene: From Energy to Biological Applications.

With the advent of a new 2D nanomaterial, namely, black phosphorus (BP) or phosphorene, the scientific community is now dedicated to focusing on and exploring this 2D material offering elusive properties such as a higher carrier mobility, biocompatibility, thickness-dependent band gap, and optoelectronic characteristics that can be harnessed for multiple applications, e.g., nanofillers, energy storage devices, field effect transistors, in water disinfection, and in biomedical sciences. The hexagonal ring of phosphorus atoms in phosphorene is twisted slightly, unlike how it is in graphene. Its unique characteristics, such as a high carrier mobility, anisotropic nature, and biocompatibility, have attracted much attention and generated further scientific curiosity. However, despite these interesting features, the phosphorene or BP poses challenges and causes frustrations when it comes to its stability under ambient conditions and processability, and thus in order to overcome these hurdles, it must be conjugated or linked with the suitable and functional organic counter macromolecule in such a way that its properties are not compromised while providing a protection from air/water that can otherwise degrade it to oxides and acid. The resulting composites/hybrid system of phosphorene and a macromolecule, e.g., a polymer, can outperform and be exploited for the aforementioned applications. These assemblies of a polymer and phosphorene have the potential for shifting the paradigm from exhaustively used graphene to new commercialized products offering multiple applications.

Dynamic Investigation of Battery Materials via Advanced Visualization: From Particle, Electrode to Cell Level.

Li-ion batteries, the most-popular secondary battery, are typically electrochemical systems controlled by ion-insertion dynamics. The battery dynamics involve mass transport, charge transfer, ion-electron coupled reactions, electrolyte penetration, ion solvation, and interfacial evolution. However, it is difficult for the traditional electrochemical methods to capture the accurate and individual details of the dynamic processes in "black box" batteries; instead, only the net result of multi-factors on the whole scale. Recently, different advanced visualization techniques have been developed, which provide powerful tools to track and monitor the internal real-time dynamic processes, giving intuitive details and fine information at various scales from crystal lattice, single particle, electrode to cell level. Here, the recent progress on the investigation of electrochemical dynamics in battery materials are reviewed, via developed techniques across wide timescales and space-scales, including the dynamic process inside the active particle, kinetics issues at the electrode/electrolyte interface, dynamic inhomogeneity in the electrode, and dynamic transportation at the cell level. Finally, the fundamental principles to improve the battery dynamics are summarized and new technologies for future more stringent conditions are highlighted. In prospect, this review opens sight on the battery interior for a clearer, deeper, and more thorough understanding of the dynamics.

Multivariate hyperspectral data analytics across length scales to probe compositional, phase, and strain heterogeneities in electrode materials.

The origins of performance degradation in batteries can be traced to atomistic phenomena, accumulated at mesoscale dimensions, and compounded up to the level of electrode architectures. Hyperspectral X-ray spectromicroscopy techniques allow for the mapping of compositional variations, and phase separation across length scales with high spatial and energy resolution. We demonstrate the design of workflows combining singular value decomposition, principal-component analysis, k-means clustering, and linear combination fitting, in conjunction with a curated spectral database, to develop high-accuracy quantitative compositional maps of the effective depth of discharge across individual positive electrode particles and ensembles of particles. Using curated reference spectra, accurate and quantitative mapping of inter- and intraparticle compositional heterogeneities, phase separation, and stress gradients is achieved for a canonical phase-transforming positive electrode material, α-V2O5. Phase maps from single-particle measurements are used to reconstruct directional stress profiles showcasing the distinctive insights accessible from a standards-informed application of high-dimensional chemical imaging.

Robust Atomic-Resolution Imaging of Lithium in Battery Materials by Center-of-Mass Scanning Transmission Electron Microscopy.

The performance of energy storage materials is often governed by their structure at the atomic scale. Conventional electron microscopy can provide detailed information about materials at these length scales, but direct imaging of light elements such as lithium presents a challenge. While several recent techniques allow lithium columns to be distinguished, these typically either involve complex contrast mechanisms that make image interpretation difficult or require significant expertise to perform. Here, we demonstrate how center-of-mass scanning transmission electron microscopy (CoM-STEM) provides an enhanced ability for simultaneous imaging of lithium and heavier element columns in lithium ion conductors. Through a combination of experiments and multislice electron scattering calculations, we show that CoM-STEM is straightforward to perform and produces directly interpretable contrast for thin samples, while being more robust to variations in experimental parameters than previously demonstrated techniques. As a result, CoM-STEM is positioned to become a reliable and facile method for directly probing all elements within energy storage materials at the atomic scale.

Exploring new battery knowledge by advanced characterizing technologies.

Exploration of science and technologies represents human's thirst for new knowledge and new life. Presently, we are in a stage of transferring the use of fossil fuels to renewable energy, which urgently calls for new energy materials and techniques beyond the boundary of human knowledge. On the way of scrutinizing these materials and surmounting the bottleneck of their performances, characterizing technologies are of critical importance in enabling the revealing of materials regarding their structural and chemical information, eventually establishing the correlations between microstructures and properties at the multiscale levels. Regrettably, traditional characterizations are hard to simultaneously probe electrochemistry with these chemical and physical structural evolutions, especially under operando conditions, or offer high-resolution images of materials sensitive to electron-beam irradiation. To this end, various advanced characterizing and diagnosing technologies recently developed, such as transmission X-ray microscopy and cryo-transmission electron microscopy, have demonstrated their benefits in understanding the energy storage behaviors of high-performance energy materials (such as layered transition oxide cathode and Li metal anode). Benefited from new knowledge, the progress of high-capacity electroactive materials is significantly accelerated. Here, we timely review the breakthroughs in emerging techniques and discuss how they guide the design of future battery materials to achieve the ultimate carbon neutrality.

Graphene Liquid Cell Electron Microscopy: Progress, Applications, and Perspectives.

Graphene liquid cell electron microscopy (GLC-EM), a cutting-edge liquid-phase EM technique, has become a powerful tool to directly visualize wet biological samples and the microstructural dynamics of nanomaterials in liquids. GLC uses graphene sheets with a one carbon atom thickness as a viewing window and a liquid container. As a result, GLC facilitates atomic-scale observation while sustaining intact liquids inside an ultra-high-vacuum transmission electron microscopy chamber. Using GLC-EM, diverse scientific results have been recently reported in the material, colloidal, environmental, and life science fields. Here, the developments of GLC fabrications, such as first-generation veil-type cells, second-generation well-type cells, and third-generation liquid-flowing cells, are summarized. Moreover, recent GLC-EM studies on colloidal nanoparticles, battery electrodes, mineralization, and wet biological samples are also highlighted. Finally, the considerations and future opportunities associated with GLC-EM are discussed to offer broad understanding and insight on atomic-resolution imaging in liquid-state dynamics.

New Insight into Desodiation/Sodiation Mechanism of MoS2: Sodium Insertion in Amorphous Mo-S Clusters.

Molybdenum disulfide (MoS2) is a promising anode material for sodium batteries due to its high theoretical capacity. While significantly improved electrochemical performance has been achieved, the reaction mechanism is still equivocal. Herein, we applied electron pair distribution function and X-ray absorption spectroscopy to investigate the desodiation/sodiation mechanism of MoS2 electrodes. The results reveal that Mo-S bonds are well preserved and dominant in the sodiation product matrix but do not convert to metallic Mo and Na2S even at deep sodiation. The MoS2 multilayer sheets break into disordered MoSx clusters with modified octahedral symmetry during discharging. The long-range order was not rebuilt during subsequent charging but with partial recovery of the Mo-S coordination symmetry. The mechanism of the reaction is independent of the carbon matrix, although it prevents the MoSx clusters from leaching into the electrolyte and thus contributes to an extended cycle life. This work refreshes the fundamental understanding of the desodiation/sodiation mechanism of MoS2 materials.

A routine for the determination of the microstructure of stacking-faulted nickel cobalt aluminium hydroxide precursors for lithium nickel cobalt aluminium oxide battery materials.

The microstructures of six stacking-faulted industrially produced cobalt- and aluminium-bearing nickel layered double hydroxide (LDH) samples that are used as precursors for Li(Ni1-x-yCo x Al y )O2 battery materials were investigated. Shifts from the brucite-type (AγB)□(AγB)□ stacking pattern to the CdCl2-type (AγB)□(CßA)□(BαC)□ and the CrOOH-type (BγA)□(AßC)□(CαB)□ stacking order, as well as random intercalation of water molecules and carbonate ions, were found to be the main features of the microstructures. A recursive routine for generating and averaging supercells of stacking-faulted layered substances implemented in the TOPAS software was used to calculate diffraction patterns of the LDH phases as a function of the degree of faulting and to refine them against the measured diffraction data. The microstructures of the precursor materials were described by a model containing three parameters: transition probabilities for generating CdCl2-type and CrOOH-type faults and a transition probability for the random intercalation of water/carbonate layers. Automated series of simulations and refinements were performed, in which the transition probabilities were modified incrementally and thus the microstructures optimized by a grid search. All samples were found to exhibit the same fraction of CdCl2-type and CrOOH-type stacking faults, which indicates that they have identical Ni, Co and Al contents. Different degrees of interstratification faulting were determined, which could be correlated to different heights of intercalation-water-related mass-loss steps in the thermal analyses.