基于金属-有机骨架的锂离子电池硅负极的研究进展

近年来,金属-有机骨架(MOFs)及其衍生物由于具有高孔隙率、可修饰的官能团、可控的化学成分等优点,在改善硅负极体积膨胀和导电性等方面取得了很大进展。通过讨论MOFs及其衍生物在锂离子电池硅负极的最新研究成果,重点阐述了以MOFs为基体的硅负极的结构设计,提出了影响其电化学性能的相关因素。最后,针对MOFs及其衍生物在电化学应用中的研究瓶颈和可能的发展方向提出看法。      

MOFs及衍生复合材料在锂硫电池中的设计应用

在能源危机与环境问题日益凸显的背景下,电化学储能技术得到了迅速发展。在“超越锂”储能领域的竞争者中,锂硫电池(Li-S)因其具有高理论比容量、高质量能量密度并且环境友好、价格低廉等优点,成为最有前途的新储能技术。但是,锂硫电池的发展仍存在一些瓶颈问题需要解决,例如正极材料导电性能差、多硫化物穿梭效应及在充放电过程中电极体积膨胀等。作为锂硫电池的关键组成部分,电极和隔膜材料的设计和制备对解决这些问题及电池整体性能提升起到了重要的作用。金属有机骨架(MOFs)及衍生的复合材料作为锂硫电池电极或隔膜修饰材料,具有质量轻、电子和离子传导性好、孔道丰富和活性位点均匀分布等优势。此外,这类复合材料还具备形貌和组分可控、来源丰富和孔径可调等特性,从而便于机制研究。本文全面介绍了锂硫电池组成、工作原理并综述了近几年MOFs及衍生复合材料在锂硫电池中的研究进展,重点讨论了其在正极材料和隔膜材料中的应用,并对未来该材料在锂硫电池研究方向上的前景和突破进行了展望。      

Hollow Metal–Organic‐Framework Micro/Nanostructures and their Derivatives: Emerging Multifunctional Materials

Hollow metal–organic framework (MOF) micro/nanostructures and their derivatives are attracting a great amount of research interest in recent years because their hierarchical porous structures not only provide abundant, easily accessed metal sites but also endow 3D channels for rapid mass transport. As a result, they demonstrate significant advantages in many applications including catalysis, gas sensors, batteries, supercapacitors, and so on. Nevertheless, studies on hollow MOFs and their derivatives are still at the beginning of this field, and the relationship between their structures and application performances is not yet reviewed comprehensively. Herein, the synthetic strategies and practical applications of hollow micro/nanostructured MOFs and their derivatives are summarized, and their corresponding prospects are also discussed.     

MXenes and their derivatives for advanced aqueous rechargeable batteries

Aqueous batteries are emerging power sources due to the merits of high safety, low cost, environmental friendliness, etc. However, several key issues such as narrow electrochemical stability window, dissolution of active materials, notorious dendrite growth and poor cycling lifespan hinder the practical application of aqueous batteries. Recently, 2D MXenes and their derivatives for aqueous batteries have exhibited substantial encouraging progress due to the special characters. The related researches have dramatically increased since 2019. However, comprehensive reviews on this topic are rare. Herein, the latest advances of MXenes and their derivatives for aqueous Zn-, Li-, Na- and dual-ion batteries are systematically reviewed, including cathode fabrication, anode design and electrolyte optimization, etc. This review aims to boost rational design strategies for practical application of aqueous batteries by combining the fundamental principle and research developments. Firstly, the fundamental background of aqueous rechargeable batteries is introduced and the superior merits for electrochemical energy storage of MXenes and their derivatives are summarized. Subsequently, the design strategies and internal mechanism of MXenes and their derivatives for aqueous batteries are comprehensively summarized and discussed. Finally, perspectives on the future design tactics of MXenes-based materials for aqueous batteries are proposed.     

Structural batteries: Advances,challenges and perspectives

The development of light-weight batteries has a great potential value for mobile applications, including electric vehicles and electric aircraft. Along with increasing energy density, another strategy for reducing battery weight is to endow energy storage devices with multifunctionality – e.g., creating an energy storage device that is able to bear structural loads and act as a replacement for structural components such that the weight of the overall system is reduced. This type of batteries is commonly referred to as “structural batteries”. Two general methods have been explored to develop structural batteries: (1) integrating batteries with light and strong external reinforcements, and (2) introducing multifunctional materials as battery components to make energy storage devices themselves structurally robust. In this review, we discuss the fundamental rules of design and basic requirements of structural batteries, summarize the progress made to date in this field, examine potential avenues and sources of inspiration for future research, and touch upon challenges remaining in this field such as safety, costs, and performance stability. Though more fundamental and technical research is needed to promote wide practical application, structural batteries show the potential to significantly improve the performance of electric vehicles and devices.     

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.     

Carbon Necklace Incorporated Electroactive Reservoir Constructing Flexible Papers for Advanced Lithium–Ion Batteries

Metal–organic frameworks (MOFs) and their derivatives with well‐defined structures and compositions show great potential for wide applications such as sensors, catalysis, energy storage, and conversion, etc. However, poor electric conductivity and large volume expansion are main obstacles for their utilization in energy storage, e.g., lithium–ion batteries and supercapacitors. Herein, a facile strategy is proposed for embedding the MOFs, e.g., ZIF‐67 and MIL‐88 into polyacrylonitrile fibers, which is further used as a template to build a 3D interconnected conductive carbon necklace paper. Owing to the unique structure features of good electric conductivity, interconnected frameworks, electroactive reservoir, and dual dopants, the obtained flexible electrodes with no additives exhibit high specific capacities, good rate capability, and prolonged cycling stability. The hollow dodecahedral ZIF‐67 derived carbon necklace paper delivers a high specific capacity of 1200 mAh g^?1 and superior stability of more than 400 cycles without capacity decay. Moreover, the spindle‐like MIL‐88 derived carbon necklace paper shows a high reversible capacity of 980 mAh g^?1. Their unique 3D interconnected structure and outstanding electrochemical performance pave the way for extending the MOF‐based interweaving materials toward potential applications in portable and wearable electronic devices.     

Road Map for In Situ Grown Binder-Free MOFs and Their Derivatives as Freestanding Electrodes for Supercapacitors

Among several electrocatalysts for energy storage purposes including supercapacitors, metal–organic frameworks (MOFs), and their derivatives have spurred wide spread interest owing to their structural merits, multifariousness with tailor-made functionalities and tunable pore sizes. The electrochemical performance of supercapacitors can be further enhanced using in situ grown MOFs and their derivatives, eliminating the role of insulating binders whose “dead mass” contribution hampers the device capability otherwise. The expulsion of binders not only ensures better adhesion of catalyst material with the current collector but also facilitates the transport of electron and electrolyte ions and remedy cycle performance deterioration with better chemical stability. This review systematically summarizes different kinds of metal–ligand combinations for in situ grown MOFs and derivatives, preparation techniques, modification strategies, properties, and charge transport mechanisms as freestanding electrode materials in determining the performance of supercapacitors. In the end, the review also highlights potential promises, challenges, and state-of-the-art advancement in the rational design of electrodes to overcome the bottlenecks and to improve the capability of MOFs in energy storage applications.     

Recent advances in electrospun carbon nanofibers and their application in electrochemical energy storage

Carbon nanofibers (CNFs) have been widely used in electrochemical energy storage devices because of their excellent conductivities, extremely large surface areas and structural stability. In energy storage devices like rechargeable batteries and supercapacitors, CNFs play multi-functional roles as active electrode materials, conductive additives and substrates for supporting active metal (oxides). Electrospinning offers a low cost and scalable technique to fabricate CNFs and their hybrids with tunable nanostructures. This paper summarizes various design strategies for producing random, aligned and core/shell structured fibers, and elucidates the influences of polymer precursors, processing parameters, conductive additives and catalysts on functional, morphological and structural characteristics of CNFs. The current start-of-the-art developments for applications in Li-ion batteries, supercapacitors, Na-ion batteries, Li–O₂ batteries and Li–S batteries are reviewed. Key issues that affect the electrochemical performance of the electrodes, such as the chemical and atomic structures, electrical conductivities, surface areas and pore size distribution of CNFs, and the particle size, shape and dispersion of metal (oxides) encapsulated in CNFs, are discussed and their solutions suggested. Future prospects on further optimization of the structure and performance, and challenges encountered in large-scale applications of electrospun CNFs are proposed.     

Metal–Organic Frameworks Based Nano/Micro/Millimeter‐Sized Self‐Propelled Autonomous Machines

Synthetic nano/micro/millimeter‐sized machines that harvest energy from the surrounding environment and then convert it to motion have had a significant impact on many research areas such as biology (sensing, imaging, and therapy) and environmental applications. Autonomous motion is a key element of these devices. A high surface area is preferable as it leads to increased propellant or cargo‐loading capability. Integrating highly ordered and porous metal–organic frameworks (MOFs) with self‐propelled machines is demonstrated to have a significant impact on the field of nano/micro/millimeter‐sized devices for a wide range of applications. MOFs have shown great potential in many research fields due to their tailorable pore size. These fields include energy storage and conversion; catalysis, biomedical application (e.g., drug delivery, imaging, and cancer therapy), and environmental remediation. The marriage of motors and MOFs may provide opportunities for many new applications for synthetic nano/micro/millimeter‐sized machines. Herein, MOF‐based micro‐ and nanomachines are reviewed with a focus on the specific properties of MOFs.     

Crossroads in the renaissance of rechargeable aqueous zinc batteries

Aqueous zinc batteries dominate the primary battery market with alkaline chemistries and recently have been rejuvenated as rechargeable devices to compete for grid-scale energy storage applications. Tremendous effort has been made in the past few years and improved cyclability has been demonstrated in both alkaline, neutral, and mild acidic systems. In this review/perspective, we will elucidate the merits of rechargeable aqueous zinc batteries through side-by-side comparison to Li-ion batteries, examine the challenges and progress made in the pursuit of highly rechargeable alkaline and mild acidic batteries, and finally provide a holistic forward look at the technology. The focus is placed on static closed cell designs, while flow batteries and open systems like zinc-air batteries will not be included due to space constraint.     

Recent Progress in Multivalent Metal (Mg,Zn, Ca,and Al) and Metal‐Ion Rechargeable Batteries with Organic Materials as Promising Electrodes

The emerging demand for electronic and transportation technologies has driven the development of rechargeable batteries with enhanced capacity storage. Especially, multivalent metal (Mg, Zn, Ca, and Al) and metal‐ion batteries have recently attracted considerable interests as promising substitutes for future large‐scale energy storage devices, due to their natural abundance and multielectron redox capability. These metals are compatible with nonflammable aqueous electrolytes and are less reactive when exposed in ambient atmosphere as compared with Li metals, hence enabling potential safer battery systems. Luckily, green and sustainable organic compounds could be designed and tailored as universal host materials to accommodate multivalent metal ions. Considering these advantages, effective approaches toward achieving organic multivalent metal and metal‐ion rechargeable batteries are highlighted in this Review. Moreover, organic structures, cell configurations, and key relevant electrochemical parameters are presented. Hopefully, this Review will provide a fundamental guidance for future development of organic‐based multivalent metal and metal‐ion rechargeable batteries.     

Chemically Integrated Inorganic‐Graphene Two‐Dimensional Hybrid Materials for Flexible Energy Storage Devices

State‐of‐the‐art energy storage devices are capable of delivering reasonably high energy density (lithium ion batteries) or high power density (supercapacitors). There is an increasing need for these power sources with not only superior electrochemical performance, but also exceptional flexibility. Graphene has come on to the scene and advancements are being made in integration of various electrochemically active compounds onto graphene or its derivatives so as to utilize their flexibility. Many innovative synthesis techniques have led to novel graphene‐based hybrid two‐dimensional nanostructures. Here, the chemically integrated inorganic‐graphene hybrid two‐dimensional materials and their applications for energy storage devices are examined. First, the synthesis and characterization of different kinds of inorganic‐graphene hybrid nanostructures are summarized, and then the most relevant applications of inorganic‐graphene hybrid materials in flexible energy storage devices are reviewed. The general design rules of using graphene‐based hybrid 2D materials for energy storage devices and their current limitations and future potential to advance energy storage technologies are also discussed.     

柔性储能电池电极的设计、制备与应用EI北大核心CSCD

随着便携式、可穿戴电子器件的迅速发展,柔性储能器件的研究逐渐转向微型化、轻柔化和智能化等方向。同时人们对器件的能量密度、功率密度和力学性能有了更高的要求。电极材料作为柔性储能器件的核心部分,是决定器件性能的关键。柔性储能电子器件的发展,又迫切需要新型电池技术和快速、低成本且可精准控制其微结构的制备方法。因此,柔性锂/钠离子电池、柔性锂硫电池、柔性锌空电池等新型储能器件的研发成为目前学术界研究的热点。本文论述了近年来柔性储能电池电极的研究现状,着重对柔性电极材料的设计(独立柔性电极和柔性基底电极)、不同维度柔性电极材料的制备工艺(一维材料、二维材料和三维材料)和柔性储能电极的应用(柔性锂/钠离子电池、柔性锂硫电池、柔性锌空电池)进行对比分析,并对电极材料的结构特性和电化学性能进行了讨论。最后,指出了柔性储能器件目前所面临的问题,并针对此类问题展望了柔性储能器件未来的重点在于新型固态电解质的研发、器件结构的合理设计及封装技术的不断优化。     

Ionic liquids for electrochemical energy storage devices applications

Ionic liquids, defined here as room-temperature molten salts, composed mainly of organic cations and (in)organic anions ions that may undergo almost unlimited structural variations with melting points below 100?°C. They offer a unique series of physical and chemical properties that make them extreme important candidates for several energy applications, especially for clean and sustainable energy storage and conversion materials and devices. Ionic liquids exhibit high thermal and electrochemical stability coupled with low volatility, create the possibility of designing appropriate electrolytes for different type batteries and supercapacitors. Herein, varieties of ionic liquids applications are reviewed on their utilization as electrolytes for Li-ion batteries, Na-ion batteries, Li-O₂(air) batteries, Li-Sulfur (Li-S) batteries, supercapacitors and as precursors to prepare and modify the electrode materials, meanwhile, some important research results in recent years are specially introduced, and the perspective on novel application of ionic liquids is also discussed.     

Materials and technologies for multifunctional,flexible or integrated supercapacitors and batteries

Electrochemical energy storage has become a key part of portable medical and electronic devices, as well as ground and aerial vehicles. Unfortunately, conventionally produced supercapacitors and batteries often cannot be easily integrated into many emerging technologies such as smart textiles, smart jewelry, paper magazines or books, and packages with data-collection or other unique capabilities, electrical cables, flexible wearable electronics and displays, flexible solar cells, epidermal sensors, and others in order to enhance their design aesthetics, convenience, system simplicity, and reliability. In addition, conventional energy storage devices that cannot conform to various shapes, are typically limited to a single function, and cannot additionally provide, for example, load bearing functionality or impact/ballistic protection to reduce the system weight or volume. Commercial devices cannot be activated by various stimuli, be able to self-destroy or biodegrade over time, trigger drug release, operate as sensors, antennas, or actuators. However, a growing number of future technologies will demand batteries and hybrid devices with the abilities to seamlessly integrate into systems and adapt to various shapes, forms, and design functions. Here we summarize recent progress and challenges made in the development of mostly nanostructured and nanoengineered materials as well as fabrication routes for energy storage devices that offer (i) multifunctionality, (ii) mechanical resiliency and flexibility and (iii) integration for more elegant, lighter, smaller and smarter designs. The geometries of device structures and materials are considered to critically define their roles in mechanics and functionality. With these understandings, we outline a future roadmap for the development, scaleup, and manufacturing of such materials and devices.     

A Universal Room-Temperature 3D Printing Approach Towards porous MOF Based Dendrites Inhibition Hybrid Solid-State Electrolytes

Hybrid solid-state electrolytes (HSSEs) provide new opportunities and inspiration for the realization of safer, higher energy-density metal batteries. The innovative application of 3‑dimensional printing in the electrochemical field, especially in solid-state electrolytes, endows energy storage devices with fascinating characteristics. In this paper, effective dendrite-inhibited PEO/MOFs HSSEs is innovatively developed through universal room-temperature 3‑dimensional printing (RT-3DP) strategy. The prepared HSSEs display enhanced dendrite inhibition due to the porous MOF filler promoting homogeneity of lithium deposition and the formation of C-OCO₃Li, ROLi, LiF mesophases, which further improve the migration of Li⁺ in PEO chain and comprehensive performances. This universal strategy realizes the fabrication of different slurry components (PEO with ZIF-67, MOF-74, UIO-66, ZIF-8 fillers) HSSEs at RT environment, providing new inspirations for the exploration of next-generation advanced solid-state batteries.     

Rechargeable aqueous zinc-ion batteries: Mechanism,design strategies and future perspectives

Rechargeable aqueous zinc-ion batteries (ZIBs) are considered to be one of the most promising energy storage devices for grid-scale applications due to their high safety, eco-friendliness, and low cost. In recent years, enormous efforts have been devoted to developing a great number of high-efficient cathodes, anodes, and electrolytes for improving the electrochemical properties of aqueous ZIBs. However, the as-documented ZIBs and their associated energy storage mechanisms are still in infancy and need to be further investigated for real practice. To expedite the development of ZIBs, this review will offer a comprehensive summary and a detailed discussion of the significant progress and breakthroughs. A brief overview of the battery configuration and various energy storage mechanisms are first introduced. The following emphasis will be mainly dedicated to discussing different design strategies regarding cathodes, anodes, and electrolytes, aiming to provide insightful design principles for future research activities from a fundamental perspective. Finally, the current challenges of developing high-performance ZIBs and their opportunities for practical viability are discussed.     

An Overview and Future Perspectives of Rechargeable Zinc Batteries

Aqueous rechargeable zinc‐based batteries have sparked a lot of enthusiasm in the energy storage field recently due to their inherent safety, low cost, and environmental friendliness. Although remarkable progress has been made in the exploration of performance so far, there are still many challenges such as low working voltage and dissolution of electrode materials at the material and system level. Herein, the central tenet is to establish a systematic summary for the construction and mechanism of different aqueous zinc‐based batteries. Details for three major zinc‐based battery systems, including alkaline rechargeable Zn‐based batteries (ARZBs), aqueous Zn ion batteries (AZIBs), and dual‐ion hybrid Zn batteries (DHZBs) are given. First, the electrode materials and energy storage mechanism of the three types of zinc‐based batteries are discussed to provide universal guidance for these batteries. Then, the electrode behavior of zinc anodes and strategies to deal with problems such as dendrite and passivation are recommended. Finally, some challenge‐oriented solutions are provided to facilitate the next development of zinc‐based batteries. Combining the characteristics of zinc‐based batteries with good use of concepts and ideas from other disciplines will surely pave the way for its commercialization.