MOF‐Derived Metal Oxide Composites for Advanced Electrochemical Energy Storage

Over the past two decades, metal–organic frameworks (MOFs), a type of porous material, have aroused great interest as precursors or templates for the derivation of metal oxides and composites for the next generation of electrochemical energy storage applications owing to their high specific surface areas, controllable structures, and adjustable pore sizes. The electrode materials, which affect the performance in practical applications, are pivotal components of batteries and supercapacitors. Metal oxide composites derived from metal–organic frameworks possessing high reversible capacity and superior rate and cycle performance are excellent electrode materials. In this Review, potential applications for MOF‐derived metal oxide composites for lithium‐ion batteries, sodium‐ion batteries, lithium–oxygen batteries, and supercapacitors are studied and summarized. Finally, the challenges and opportunities for future research on MOF‐derived metal oxide composites are proposed on the basis of academic knowledge from the reported literature as well as from experimental experience.     

Complex Nanostructures from Materials based on Metal–Organic Frameworks for Electrochemical Energy Storage and Conversion

Metal–organic frameworks (MOFs) have drawn tremendous attention because of their abundant diversity in structure and composition. Recently, there has been growing research interest in deriving advanced nanomaterials with complex architectures and tailored chemical compositions from MOF‐based precursors for electrochemical energy storage and conversion. Here, a comprehensive overview of the synthesis and energy‐related applications of complex nanostructures derived from MOF‐based precursors is provided. After a brief summary of synthetic methods of MOF‐based templates and their conversion to desirable nanostructures, delicate designs and preparation of complex architectures from MOFs or their composites are described in detail, including porous structures, single‐shelled hollow structures, and multishelled hollow structures, as well as other unusual complex structures. Afterward, their applications are discussed as electrode materials or catalysts for lithium‐ion batteries, hybrid supercapacitors, water‐splitting devices, and fuel cells. Lastly, the research challenges and possible development directions of complex nanostructures derived from MOF‐based‐templates for electrochemical energy storage and conversion applications are outlined.     

The Application of Hollow Structured Anodes for Sodium‐Ion Batteries: From Simple to Complex Systems

Hollow structures exhibit fascinating and important properties for energy‐related applications, such as lithium‐ion batteries, supercapacitors, and electrocatalysts. Sodium‐ion batteries, as analogs of lithium‐ion batteries, are considered as promising devices for large‐scale electrical energy storage. Inspired by applications of hollow structures as anodes for lithium‐ion batteries, the application of these structures in sodium‐ion batteries has attracted great attention in recent years. However, due to the difference in lithium and sodium‐ion batteries, there are several issues that need to be addressed toward rational design of hollow structured sodium anodes. Herein, this research news article presents the recent developments in the synthesis of hollow structured anodes for sodium‐ion batteries. The main strategies for rational design of materials for sodium‐ion batteries are presented to provide an overview and perspectives for the future developments of this research area.     

Current Status and Future Prospects of Metal–Sulfur Batteries

Lithium–sulfur batteries are a major focus of academic and industrial energy‐storage research due to their high theoretical energy density and the use of low‐cost materials. The high energy density results from the conversion mechanism that lithium–sulfur cells utilize. The sulfur cathode, being naturally abundant and environmentally friendly, makes lithium–sulfur batteries a potential next‐generation energy‐storage technology. The current state of the research indicates that lithium–sulfur cells are now at the point of transitioning from laboratory‐scale devices to a more practical energy‐storage application. Based on similar electrochemical conversion reactions, the low‐cost sulfur cathode can be coupled with a wide range of metallic anodes, such as sodium, potassium, magnesium, calcium, and aluminum. These new “metal–sulfur” systems exhibit great potential in either lowering the production cost or producing high energy density. Inspired by the rapid development of lithium–sulfur batteries and the prospect of metal–sulfur cells, here, over 450 research articles are summarized to analyze the research progress and explore the electrochemical characteristics, cell‐assembly parameters, cell‐testing conditions, and materials design. In addition to highlighting the current research progress, the possible future areas of research which are needed to bring conversion‐type lithium–sulfur and other metal–sulfur batteries into the market are also discussed.     

Hollow MXene Spheres and 3D Macroporous MXene Frameworks for Na‐Ion Storage

2D transition metal carbides and nitrides, named MXenes, are attracting increasing attentions and showing competitive performance in energy storage devices including electrochemical capacitors, lithium‐ and sodium‐ion batteries, and lithium–sulfur batteries. However, similar to other 2D materials, MXene nanosheets are inclined to stack together, limiting the device performance. In order to fully utilize MXenes' electrochemical energy storage capability, here, processing of 2D MXene flakes into hollow spheres and 3D architectures via a template method is reported. The MXene hollow spheres are stable and can be easily dispersed in solvents such as water and ethanol, demonstrating their potential applications in environmental and biomedical fields as well. The 3D macroporous MXene films are free‐standing, flexible, and highly conductive due to good contacts between spheres and metallic conductivity of MXenes. When used as anodes for sodium‐ion storage, these 3D MXene films exhibit much improved performances compared to multilayer MXenes and MXene/carbon nanotube hybrid architectures in terms of capacity, rate capability, and cycling stability. This work demonstrates the importance of MXene electrode architecture on the electrochemical performance and can guide future work on designing high‐performance MXene‐based materials for energy storage, catalysis, environmental, and biomedical applications.     

Porous Graphene Materials for Advanced Electrochemical Energy Storage and Conversion Devices

Combining the advantages from both porous materials and graphene, porous graphene materials have attracted vast interests due to their large surface areas, unique porous structures, diversified compositions and excellent electronic conductivity. These unordinary features enable porous graphene materials to serve as key components in high‐performance electrochemical energy storage and conversion devices such as lithium ion batteries, supercapacitors, and fuel cells. This progress report summarizes the typical fabrication methods for porous graphene materials with micro‐, meso‐, and macro‐porous structures. The structure–property relationships of these materials and their application in advanced electrochemical devices are also discussed.     

Hierarchical Interconnected Expanded Graphitic Ribbons Embedded with Amorphous Carbon: An Advanced Carbon Nanostructure for Superior Lithium and Sodium Storage

Carbon materials have attracted considerable attention as anodes for lithium‐ion and sodium‐ion batteries due to their low cost and environmental friendliness. This work reports an advanced carbon nanostructure that takes advantage of the chelation effect of glucose and metal ions, which ensures the uniform dispersion of metal in the precursor. Thus, an effective catalytic conversion from sp³ to sp² carbon occurs, enabling simultaneously formation of pores with catalyzed graphitic structures. Due to the low carbonization temperature and short carbonization time as well as the different catalytic degree of various metals, a series of expanded graphitic layers from 0.34 to 0.44 nm with defects and amorphous carbon structure are obtained. The structure not only offers accessible graphitic spacings for reversible lithium/sodium ion insertion, but also provides abundant active sites for lithium/sodium ion adsorption in the defects and amorphous structure. Moreover, the hierarchical interconnected porous structure combining graphitic ribbons is beneficial for fast electronic/ionic transport and favorable electrolyte permeation. More importantly, such advanced carbon materials prove their feasibility for balancing the pore structure and degree of graphitization. When serving as the electrode material for lithium‐ion and sodium‐ion batteries, excellent electrochemical performance along with fast kinetics and long cycle life is achieved.     

金属氰胺化合物的结构、合成及电化学储能应用

金属氰胺化合物M_x(NCN)_y作为类氧硫族化合物, 是一类新兴的无机功能材料。准线性[NCN]^2-阴离子赋予其空旷和具有孔道的晶体结构、独特的电子结构和新奇的物化性质, 金属氰胺化合物在固态发光、光/电催化及电化学储能等诸多领域展现出应用前景, 近年来逐渐成为研究热点。本文简要回顾了金属氰胺化合物的研究历史, 概述了金属氰胺化合物的晶体结构及物化性质, 总结了常见合成方法及策略, 探讨了金属氰胺化合物在电化学储能领域的应用, 重点论述了其作为锂钠离子电池新型负极材料的电化学性能及存储机制。     

Wet‐Chemical Synthesis of Hollow Red‐Phosphorus Nanospheres with Porous Shells as Anodes for High‐Performance Lithium‐Ion and Sodium‐Ion Batteries

Large‐volume‐expansion‐induced material pulverization severely limits the electrochemical performance of red phosphorous (P) for energy‐storage applications. Hollow nanospheres with porous shells are recognized as an ideal structure to resolve these issues. However, a chemical synthetic approach for preparing nanostructured red P is always of great challenge and hollow nanosphere structures of red P have not yet been fabricated. Herein, a wet solvothermal method to successfully fabricate hollow P nanospheres (HPNs) with porous shells via a gas‐bubble‐directed formation mechanism is developed. More importantly, due to the merits of the porous and hollow structures, these HPNs reveal the highest capacities (based on the weight of electrode materials) of 1285.7 mA h g^?1 for lithium‐ion batteries and 1364.7 mA h g^?1 for sodium‐ion batteries at 0.2 C, and excellent long‐cycling performance.     

Hollow Functional Materials Derived from Metal–Organic Frameworks: Synthetic Strategies,Conversion Mechanisms,and Electrochemical Applications

Hollow materials derived from metal–organic frameworks (MOFs), by virtue of their controllable configuration, composition, porosity, and specific surface area, have shown fascinating physicochemical properties and widespread applications, especially in electrochemical energy storage and conversion. Here, the recent advances in the controllable synthesis are discussed, mainly focusing on the conversion mechanisms from MOFs to hollow‐structured materials. The synthetic strategies of MOF‐derived hollow‐structured materials are broadly sorted into two categories: the controllable synthesis of hollow MOFs and subsequent pyrolysis into functional materials, and the controllable conversion of solid MOFs with predesigned composition and morphology into hollow structures. Based on the formation processes of hollow MOFs and the conversion processes of solid MOFs, the synthetic strategies are further conceptually grouped into six categories: template‐mediated assembly, stepped dissolution–regrowth, selective chemical etching, interfacial ion exchange, heterogeneous contraction, and self‐catalytic pyrolysis. By analyzing and discussing 14 types of reaction processes in detail, a systematic mechanism of conversion from MOFs to hollow‐structured materials is exhibited. Afterward, the applications of these hollow structures as electrode materials for lithium‐ion batteries, hybrid supercapacitors, and electrocatalysis are presented. Finally, an outlook on the emergent challenges and future developments in terms of their controllable fabrications and electrochemical applications is further discussed.     

Applications of Metal–Organic‐Framework‐Derived Carbon Materials

Carbon materials derived from metal–organic frameworks (MOFs) have attracted much attention in the field of scientific research in recent years because of their advantages of excellent electron conductivity, high porosity, and diverse applications. Tremendous efforts are devoted to improving their chemical and physical properties, including optimizing the morphology and structure of the carbon materials, compositing them with other materials, and so on. Here, many kinds of carbon materials derived from metal–organic frameworks are introduced with a particular focus on their promising applications in batteries (lithium‐ion batteries, lithium–sulfur batteries, and sodium‐ion batteries), supercapacitors (metal oxide/carbon and metal sulfide/carbon), electrocatalytic reactions (oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction), water treatment (MOF‐derived carbon and other techniques), and other possible fields. To close, some existing problem and corresponding possible solutions are proposed based on academic knowledge from the reported literature, along with a great deal of experimental experience.     

Focus on Spinel Li4Ti5O12 as Insertion Type Anode for High‐Performance Na‐Ion Batteries

Sodium‐ion batteries (SIBs) toward large‐scale energy storage applications has fascinated researchers in recent years owing to the low cost, environmental friendliness, and inestimable abundance. The similar chemical and electrochemical properties of sodium and lithium make sodium an easy substitute for lithium in lithium‐ion batteries. However, the main issues of limited cycle life, low energy density, and poor power density hamper the commercialization process. In the last few years, the development of electrode materials for SIBs has been dedicated to improving sodium storage capacities, high energy density, and long cycle life. The insertion type spinel Li₄Ti₅O₁₂ (LTO) possesses “zero‐strain” behavior that offers the best cycle life performance among all reported oxide‐based anodes, displaying a capacity of 155 mAh g^?1 via a three‐phase separation mechanism, and competing for future topmost high energy anode for SIBs. Recent reports offer improvement of overall electrode performance through carbon coating, doping, composites with metal oxides, and surface modification techniques, etc. Further, LTO anode with its structure and properties for SIBs is described and effective methods to improve the LTO performance are discussed in both half‐cell and practical configuration, i.e., full‐cell, along with future perspectives and solutions to promote its use.     

Composite‐Structure Material Design for High‐Energy Lithium Storage

High‐energy storage devices are in demand for the rapid development of modern society. Until now, many kinds of energy storage devices, such as lithium‐ion batteries (LIBs), sodium‐ion batteries (NIBs), and so on, have been developed in the past 30 years. However, most of the commercially exploited and studied active electrode materials of these energy storage devices possess a single phase with low reversible capacity or unsatisfied cycle stability. Continuous and extensive research efforts are made to develop alternative materials with a higher specific energy density and long cycle life by element doping or surface modification. A novel strategy of forming composite‐structure electrode materials by introducing structure units has attracted great attention in recent years. Herein, based on previous publications on these composite‐structure materials, some important scientific points focusing on the design of composite‐structure materials for better electrochemical performances reveal the distinction of composite structures based on average and local structure analysis methods, and an understanding of the relationship between these interior composite structures and their electrochemical performances is discussed thoroughly. The lithiation/delithiation mechanism and the remaining challenges and perspectives for composite‐structure electrode materials are also elaborated.     

Ti‐Based Oxide Anode Materials for Advanced Electrochemical Energy Storage: Lithium/Sodium Ion Batteries and Hybrid Pseudocapacitors

Titanium‐based oxides including TiO₂ and M‐Ti‐O compounds (M = Li, Nb, Na, etc.) family, exhibit advantageous structural dynamics (2D ion diffusion path, open and stable structure for ion accommodations) for practical applications in energy storage systems, such as lithium‐ion batteries, sodium‐ion batteries, and hybrid pseudocapacitors. Further, Ti‐based oxides show high operating voltage relative to the deposition of alkali metal, ensuring full safety by avoiding the formation of lithium and sodium dendrites. On the other hand, high working potential prevents the decomposition of electrolyte, delivering excellent rate capability through the unique pseudocapacitive kinetics. Nevertheless, the intrinsic poor electrical conductivity and reaction dynamics limit further applications in energy storage devices. Recently, various work and in‐depth understanding on the morphologies control, surface engineering, bulk‐phase doping of Ti‐based oxides, have been promoted to overcome these issues. Inspired by that, in this review, the authors summarize the fundamental issues, challenges and advances of Ti‐based oxides in the applications of advanced electrochemical energy storage. Particularly, the authors focus on the progresses on the working mechanism and device applications from lithium‐ion batteries to sodium‐ion batteries, and then the hybrid pseudocapacitors. In addition, future perspectives for fundamental research and practical applications are discussed.     

Nanoarchitectured Design of Porous Materials and Nanocomposites from Metal‐Organic Frameworks

The emergence of metal‐organic frameworks (MOFs) as a new class of crystalline porous materials is attracting considerable attention in many fields such as catalysis, energy storage and conversion, sensors, and environmental remediation due to their controllable composition, structure and pore size. MOFs are versatile precursors for the preparation of various forms of nanomaterials as well as new multifunctional nanocomposites/hybrids, which exhibit superior functional properties compared to the individual components assembling the composites. This review provides an overview of recent developments achieved in the fabrication of porous MOF‐derived nanostructures including carbons, metal oxides, metal chalcogenides (metal sulfides and selenides), metal carbides, metal phosphides and their composites. Finally, the challenges and future trends and prospects associated with the development of MOF‐derived nanomaterials are also examined.     

Carbon‐Based Alloy‐Type Composite Anode Materials toward Sodium‐Ion Batteries

In the scenario of renewable clean energy gradually replacing fossil energy, grid‐scale energy storage systems are urgently necessary, where Na‐ion batteries (SIBs) could supply crucial support, due to abundant Na raw materials and a similar electrochemical mechanism to Li‐ion batteries. The limited energy density is one of the major challenges hindering the commercialization of SIBs. Alloy‐type anodes with high theoretical capacities provide good opportunities to address this issue. However, these anodes suffer from the large volume expansion and inferior conductivity, which induce rapid capacity fading, poor rate properties, and safety issues. Carbon‐based alloy‐type composites (CAC) have been extensively applied in the effective construction of anodes that improved electrochemical performance, as the carbon component could alleviate the volume change and increase the conductivity. Here, state‐of‐the‐art CAC anode materials applied in SIBs are summarized, including their design principle, characterization, and electrochemical performance. The corresponding alloying mechanism along with its advantages and disadvantages is briefly presented. The crucial roles and working mechanism of the carbon matrix in CAC anodes are discussed in depth. Lastly, the existing challenges and the perspectives are proposed. Such an understanding critically paves the way for tailoring and designing suitable alloy‐type anodes toward practical applications.     

Nanoscale Engineering of Heterostructured Anode Materials for Boosting Lithium‐Ion Storage

Rechargeable lithium‐ion batteries (LIBs), as one of the most important electrochemical energy‐storage devices, currently provide the dominant power source for a range of devices, including portable electronic devices and electric vehicles, due to their high energy and power densities. The interest in exploring new electrode materials for LIBs has been drastically increasing due to the surging demands for clean energy. However, the challenging issues essential to the development of electrode materials are their low lithium capacity, poor rate ability, and low cycling stability, which strongly limit their practical applications. Recent remarkable advances in material science and nanotechnology enable rational design of heterostructured nanomaterials with optimized composition and fine nanostructure, providing new opportunities for enhancing electrochemical performance. Here, the progress as to how to design new types of heterostructured anode materials for enhancing LIBs is reviewed, in the terms of capacity, rate ability, and cycling stability: i) carbon‐nanomaterials‐supported heterostructured anode materials; ii) conducting‐polymer‐coated electrode materials; iii) inorganic transition‐metal compounds with core@shell structures; and iv) combined strategies to novel heterostructures. By applying different strategies, nanoscale heterostructured anode materials with reduced size, large surfaces area, enhanced electronic conductivity, structural stability, and fast electron and ion transport, are explored for boosting LIBs in terms of high capacity, long cycling lifespan, and high rate durability. Finally, the challenges and perspectives of future materials design for high‐performance LIB anodes are considered. The strategies discussed here not only provide promising electrode materials for energy storage, but also offer opportunities in being extended for making a variety of novel heterostructured nanomaterials for practical renewable energy applications.     

Research Advances of Amorphous Metal Oxides in Electrochemical Energy Storage and Conversion

Amorphous metal oxides (AMOs) have aroused great enthusiasm across multiple energy areas over recent years due to their unique properties, such as the intrinsic isotropy, versatility in compositions, absence of grain boundaries, defect distribution, flexible nature, etc. Here, the materials engineering of AMOs is systematically reviewed in different electrochemical applications and recent advances in understanding and developing AMO‐based high‐performance electrodes are highlighted. Attention is focused on the important roles that AMOs play in various energy storage and conversion technologies, such as active materials in metal‐ion batteries and supercapacitors as well as active catalysts in water splitting, metal–air batteries, and fuel cells. The improvements of electrochemical performance in metal‐ion batteries and supercapacitors are reviewed regarding the enhancement in active sites, mechanical strength, and defect distribution of amorphous structures. Furthermore, the high electrochemical activities boosted by AMOs in various fundamental reactions are elaborated on and they are related to the electrocatalytic behaviors in water splitting, metal–air batteries, and fuel cells. The applications in electrochromism and high‐conducting sensors are also briefly discussed. Finally, perspectives on the existing challenges of AMOs for electrochemical applications are proposed, together with several promising future research directions.     

Lithiophilic 3D Nanoporous Nitrogen‐Doped Graphene for Dendrite‐Free and Ultrahigh‐Rate Lithium‐Metal Anodes

The key bottlenecks hindering the practical implementations of lithium‐metal anodes in high‐energy‐density rechargeable batteries are the uncontrolled dendrite growth and infinite volume changes during charging and discharging, which lead to short lifespan and catastrophic safety hazards. In principle, these problems can be mitigated or even solved by loading lithium into a high‐surface‐area, conductive, and lithiophilic porous scaffold. However, a suitable material that can synchronously host a large loading amount of lithium and endure a large current density has not been achieved. Here, a lithiophilic 3D nanoporous nitrogen‐doped graphene as the sought‐after scaffold material for lithium anodes is reported. The high surface area, large porosity, and high conductivity of the nanoporous graphene concede not only dendrite‐free stripping/plating but also abundant open space accommodating volume fluctuations of lithium. This ingenious scaffold endows the lithium composite anode with a long‐term cycling stability and ultrahigh rate capability, significantly improving the charge storage performance of high‐energy‐density rechargeable lithium batteries.     

Layered Transition Metal Dichalcogenide-Based Nanomaterials for Electrochemical Energy Storage

The rapid development of electrochemical energy storage (EES) systems requires novel electrode materials with high performance. A typical 2D nanomaterial, layered transition metal dichalcogenides (TMDs) are regarded as promising materials used for EES systems due to their large specific surface areas and layer structures benefiting fast ion transport. The typical methods for the preparation of TMDs and TMD-based nanohybrids are first summarized. Then, in order to improve the electrochemical performance of various kinds of rechargeable batteries, such as lithium-ion batteries, lithium–sulfur batteries, sodium-ion batteries, and other types of emerging batteries, the strategies for the design and fabrication of layered TMD-based electrode materials are discussed. Furthermore, the applications of layered TMD-based nanomaterials in supercapacitors, especially in untraditional supercapacitors, are presented. Finally, the existing challenges and promising future research directions in this field are proposed.