导电基质纳米复合电极材料的研究进展

在各种能源储存设备中,锂离子电池成为重要的首选储能器件,在便携电子设备、电动车、混合电动车及其它能源存储设备等方面都有广泛应用。如何提高锂离子电池用电极材料的锂离子储存性能,已经成为材料科学与工程领域的热点之一。利用导电基质构建纳米结构复合材料是提高锂离子储存性能的有效途径。简要介绍了碳基和金属基质纳米复合电极材料的研究进展,主要包括材料制备新方法、新工艺、锂离子电池改性及其发展趋势等内容。     

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.     

生物模板法合成锂离子电池电极材料研究进展

锂离子电池是一类极具潜力的新型二次化学储能器件,被广泛应用于便携式电子设备、电动交通工具和智能电网等领域。高性能电极材料的设计和合成是获得高能量密度、长循环寿命、高安全性锂离子电池的关键。文章针对锂离子电池电极材料存在制备工艺复杂、结构难以控制、活性物质利用率低、循环稳定性和倍率性能差等问题,从生物资源高效利用角度出发,结合生物材料尺寸均匀、形态多变、结构精密、环境友好等优点,综述了生物模板法合成锂离子电池电极材料的研究进展,并对该领域的发展方向进行了展望。     

Nanostructured electrodes for lithium-ion and lithium-air batteries: the latest developments, challenges, and perspectives

The urgency for clean and secure energy has stimulated a global resurgence in searching for advanced electrical energy storage systems. For now and the foreseeable future, batteries remain the most promising electrical energy storage systems for many applications, from portable electronics to emerging technologies such as electric vehicles and smart grids, by potentially offering significantly improved performance, energy efficiencies, reliability, and energy security while also permitting a drastic reduction in fuel consumption and emissions. The energy and power storage characteristics of batteries critically impact the commercial viability of these emerging technologies. For example, the realization of electric vehicles hinges on the availability of batteries with significantly improved energy and power density, durability, and reduced cost. Further, the design, performance, portability, and innovation of many portable electronics are limited severely by the size, power, and cycle life of the existing batteries. Creation of nanostructured electrode materials represents one of the most attractive strategies to dramatically enhance battery performance, including capacity, rate capability, cycling life, and safety. This review aims at providing the reader with an understanding of the critical scientific challenges facing the development of advanced batteries, various unique attributes of nanostructures or nano-architectures applicable to lithium-ion and lithium-air batteries, the latest developments in novel synthesis and fabrication procedures, the unique capabilities of some powerful, in situ characterization techniques vital to unraveling the mechanisms of charge and mass transport processes associated with battery performance, and the outlook for future-generation batteries that exploit nanoscale materials for significantly improved performance to meet the ever-increasing demands of emerging technologies.     

Recent progress in cathode materials research for advanced lithium ion batteries

New and improved materials for energy storage are urgently required to make more efficient use of our finite supply of fossil fuels, and to enable the effective use of renewable energy sources. Lithium ion batteries (LIB) are a key resource for mobile energy, and one of the most promising solutions for environment-friendly transportation such as plug-in hybrid electric vehicles (PHEVs). Among the three key components (cathode, anode and electrolyte) of LIB, cathode material is usually the most expensive one with highest weight in the battery, which justifies the intense research focus on this electrode. In this review, we present an overview of the breakthroughs in the past decade in developing high energy high power cathode materials for lithium ion batteries. Materials from six structural groups (layered oxides, spinel oxides, olivine compounds, silicate compounds, tavorite compounds, and borate compounds) are covered. We focus on their electrochemical performances and the related fundamental crystal structures, solid-state physics and chemistry are covered. The effect of modifications on both chemistry and morphology are discussed as well.     

Functional materials for rechargeable batteries

There is an ever-growing demand for rechargeable batteries with reversible and efficient electrochemical energy storage and conversion. Rechargeable batteries cover applications in many fields, which include portable electronic consumer devices, electric vehicles, and large-scale electricity storage in smart or intelligent grids. The performance of rechargeable batteries depends essentially on the thermodynamics and kinetics of the electrochemical reactions involved in the components (i.e., the anode, cathode, electrolyte, and separator) of the cells. During the past decade, extensive efforts have been dedicated to developing advanced batteries with large capacity, high energy and power density, high safety, long cycle life, fast response, and low cost. Here, recent progress in functional materials applied in the currently prevailing rechargeable lithium-ion, nickel-metal hydride, lead acid, vanadium redox flow, and sodium-sulfur batteries is reviewed. The focus is on research activities toward the ionic, atomic, or molecular diffusion and transport; electron transfer; surface/interface structure optimization; the regulation of the electrochemical reactions; and the key materials and devices for rechargeable batteries.     

A Zinc–Dual-Halogen Battery with a Molten Hydrate Electrolyte

Halogen redox couples offer several advantages for energy storage such as low cost, high solubility in water, and high redox potential. However, the operational complexity of storing halogens at the oxidation state via liquid-phase media hampers their widespread application in energy-storage devices. Herein, an aqueous zinc–dual-halogen battery system taking the advantages of redox flow batteries (inherent scalability) and intercalation chemistry (high capacity) is designed and fabricated. To enhance specific energy, the designed cell exploits both bromine and chlorine as the cathode redox couples that are present as halozinc complexes in a newly developed molten hydrate electrolyte, which is distinctive to the conventional zinc–bromine batteries. Benefiting from the reversible uptake of halogens at the graphite cathode, exclusive reliance on earth-abundant elements, and membrane-free and possible flow-through configuration, the proposed battery can potentially realize high-performance massive electric energy storage at a reasonable cost.     

Molten salts for rechargeable batteries

The growing demand of advanced electrochemical energy storage devices for various applications, including portable electronic products, electric vehicles, and large-scale energy storage grids, has triggered extensive research interests and efforts on various rechargeable batteries such as lithium/sodium-ion batteries (LIBs/NIBs), aluminium-ion batteries (AIBs), liquid metal batteries (LMBs), and molten-air batteries (MABs) in the past decades. A key issue to push forward the development of these batteries is the exploration of high-performance electrodes and electrolytes, which calls for efficient and versatile synthetic methods. Molten salts (MSs), liquid-phase ionic compounds or mixtures, provide an effective platform to widen the reaction temperatures and enrich the chemical environments for the synthesis of novel electrode materials and electrolytes. In this review, the general principles of molten salts and recent research progresses on molten salt-based battery materials are surveyed. Molten-salt synthesis of electrode materials, including sintering and electrolysis, are emerging as competitive substitutes for conventional synthesis techniques. These methods have shown their effectiveness and uniqueness in adjusting the crystal structure, morphology, and performance of electrode materials for LIBs/NIBs, as suggested by recent progresses and applications of diverse cathodes (layered oxides, spinel oxides, polyanions, etc.) and anodes (metal oxides, alloys, carbons, etc.). Furthermore, the applications of molten salts as effective electrolytes are demonstrated in representative new-type secondary batteries including AIBs, LMBs and MABs. Finally, the emerging opportunities, challenges, and interesting research trends are envisioned to promote the further development of molten-salt methodology for rechargeable batteries.     

Advanced Materials for Energy Storage

Popularization of portable electronics and electric vehicles worldwide stimulates the development of energy storage devices, such as batteries and supercapacitors, toward higher power density and energy density, which significantly depends upon the advancement of new materials used in these devices. Moreover, energy storage materials play a key role in efficient, clean, and versatile use of energy, and are crucial for the exploitation of renewable energy. Therefore, energy storage materials cover a wide range of materials and have been receiving intensive attention from research and development to industrialization. In this Review, firstly a general introduction is given to several typical energy storage systems, including thermal, mechanical, electromagnetic, hydrogen, and electrochemical energy storage. Then the current status of high‐performance hydrogen storage materials for on‐board applications and electrochemical energy storage materials for lithium‐ion batteries and supercapacitors is introduced in detail. The strategies for developing these advanced energy storage materials, including nanostructuring, nano‐/microcombination, hybridization, pore‐structure control, configuration design, surface modification, and composition optimization, are discussed. Finally, the future trends and prospects in the development of advanced energy storage materials are highlighted.     

The applications of zeolitic imidazolate framework-8 in electrical energy storage devices: a review

In order to meet the requirement of electric vehicles (EVs), hybrid electric vehicles (HEVs) and smart grids, effective energy storage devices will become imperative in the future energy technologies. However, it is necessary to further improve the energy density, rate performance and cycle performance of the energy storage devices. Zeolitic imidazolate framework-8 (ZIF-8) is a kind of porous materials that has attracted enormous attention due to its high surface areas, controllable structures and tunable pore sizes. Besides the applications in gas storage and separation, catalysis, sensor, and drug delivery, ZIF-8 is receiving increasing research interest in the field of electrochemical energy storage due to the advantage of synthetic method, such as simplicity and safety. By focusing on recent advances, we summarize the applications of ZIF-8 in electrical energy storage devices, such as rechargeable batteries and supercapacitors. We also list the current problems in applications and give the future study direction.     

锂硫电池硫正极材料研究进展

由化石燃料的大量使用导致的全球能源和环境问题日益严重,已对人们的生产和生活产生了明显的影响.开发利用储量丰富的清洁能源(如太阳能、水能和风能等)有望较好地解决全球能源和环境问题.由于这些清洁能源存在地域性、间歇性等特点,高效的能量转化和存储技术是实现清洁能源规模化利用的关键和基础.锂离子电池作为绿色环保的储能器件,已在手机、笔记本电脑、相机等便携电子产品中广泛使用.近年来,锂离子电池开始在电动汽车等动力电池领域得到应用.但是,由于其能量密度不够高,导致锂离子电池电动汽车续航短、充电频繁及购车成本高.由金属锂为负极和硫为正极组成的锂硫电池的能量密度(2600 Wh·kg-1)远高于目前广泛使用的锂离子电池.此外,硫正极材料具有储量丰富、毒性低、价格便宜、环境友好等突出优点.因此,锂硫电池被认为是当前最具研究前景的高能量密度二次电池之一.硫正极材料的本征导电性差、在充放电过程中存在较大的体积膨胀和收缩,储放锂过程中形成的多硫化锂易溶于电解液,使得锂硫电池的倍率性能、循环寿命和库伦效率等电化学性能离实际应用仍有较大距离.迄今为止,关于硫正极材料的研究工作,主要集中于如何提升其导电性、抑制或消除由多硫化锂的溶解引起的穿梭效应以及在反复的循环过程中保持电极材料微结构的稳定性等方面.相关研究表明,将硫与不同形貌的碳材料复合构筑成具有特殊微观结构的硫/碳复合正极材料可显著提高其导电性、抑制多硫化锂的穿梭效应和减缓储放锂前后的体积变化,进而改善倍率性能、循环稳定性和充放电效率等.此外,在硫正极材料中引入异质元素掺杂碳材料、金属氧化物和导电集合物均可通过化学吸附实现对易溶解多硫化锂的有效吸附.将上述多种改性方法结合也可使硫正极材料具有优异的电化学储锂性能.本文从锂硫电池的工作原理出发,总结了硫正极材料存在的主要问题,综述了近几年锂硫电池复合正极材料的研究进展,最后对锂硫电池正极材料的研究思路与发展趋势进行了分析和展望.     

Toward High-Energy-Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes

With increasing demands for safe, high capacity energy storage to support personal electronics, newer devices such as unmanned aerial vehicles, as well as the commercialization of electric vehicles, current energy storage technologies are facing increased challenges. Although alternative batteries have been intensively investigated, lithium (Li) batteries are still recognized as the preferred energy storage solution for the consumer electronics markets and next generation automobiles. However, the commercialized Li batteries still have disadvantages, such as low capacities, potential safety issues, and unfavorable cycling life. Therefore, the design and development of electromaterials toward high-energy-density, long-life-span Li batteries with improved safety is a focus for researchers in the field of energy materials. Herein, recent advances in the development of novel organic electrolytes are summarized toward solid-state Li batteries with higher energy density and improved safety. On the basis of new insights into ionic conduction and design principles of organic-based solid-state electrolytes, specific strategies toward developing these electrolytes for Li metal anodes, high-energy-density cathode materials (e.g., high voltage materials), as well as the optimization of cathode formulations are outlined. Finally, prospects for next generation solid-state electrolytes are also proposed.     

Polymer-Based Batteries—Flexible and Thin Energy Storage Systems

Batteries have become an integral part of everyday life—from small coin cells to batteries for mobile phones, as well as batteries for electric vehicles and an increasing number of stationary energy storage applications. There is a large variety of standardized battery sizes (e.g., the familiar AA-battery or AAA-battery). Interestingly, all these battery systems are based on a huge number of different cell chemistries depending on the application and the corresponding requirements. There is not one single battery type fulfilling all demands for all imaginable applications. One battery class that has been gaining significant interest in recent years is polymer-based batteries. These batteries utilize organic materials as the active parts within the electrodes without utilizing metals (and their compounds) as the redox-active materials. Such polymer-based batteries feature a number of interesting properties, like high power densities and flexible batteries fabrication, among many more.     

Flexible 1D Batteries: Recent Progress and Prospects

With the rapid development of wearable and portable electronics, flexible and stretchable energy storage devices to power them are rapidly emerging. Among numerous flexible energy storage technologies, flexible batteries are considered as the most favorable candidate due to their high energy density and long cycle life. In particular, flexible 1D batteries with the unique advantages of miniaturization, adaptability, and weavability are expected to be a part of such applications. The development of 1D batteries, including lithium-ion batteries, zinc-ion batteries, zinc–air batteries, and lithium–air batteries, is comprehensively summarized, with particular emphasis on electrode preparation, battery design, and battery properties. In addition, the remaining challenges to the commercialization of current 1D batteries and prospective opportunities in the field are discussed.     

7Li MRI of Li batteries reveals location of microstructural lithium

There is an ever-increasing need for advanced batteries for portable electronics, to power electric vehicles and to facilitate the distribution and storage of energy derived from renewable energy sources. The increasing demands on batteries and other electrochemical devices have spurred research into the development of new electrode materials that could lead to better performance and lower cost (increased capacity, stability and cycle life, and safety). These developments have, in turn, given rise to a vigorous search for the development of robust and reliable diagnostic tools to monitor and analyse battery performance, where possible, in situ. Yet, a proven, convenient and non-invasive technology, with an ability to image in three dimensions the chemical changes that occur inside a full battery as it cycles, has yet to emerge. Here we demonstrate techniques based on magnetic resonance imaging, which enable a completely non-invasive visualization and characterization of the changes that occur on battery electrodes and in the electrolyte. The current application focuses on lithium-metal batteries and the observation of electrode microstructure build-up as a result of charging. The methods developed here will be highly valuable in the quest for enhanced battery performance and in the evaluation of other electrochemical devices.     

Recent Advances in Energy Chemical Engineering of Next-Generation Lithium Batteries

Rechargeable lithium-ion batteries (LIBs) afford a profound impact on our modern daily life. However, LIBs are approaching the theoretical energy density, due to the inherent limitations of intercalation chemistry; thus, they cannot further satisfy the increasing demands of portable electronics, electric vehicles, and grids. Therefore, battery chemistries beyond LIBs are being widely investigated. Next-generation lithium (Li) batteries, which employ Li metal as the anode and intercalation or conversion materials as the cathode, receive the most intensive interest due to their high energy density and excellent potential for commercialization. Moreover, significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions, as well as to technological improvement. This review starts by summarizing the electrolytes for next-generation Li batteries. Key challenges and recent progress in lithium-ion, lithium–sulfur, and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science. Finally, possible directions for further development in Li batteries are presented. Next-generation Li batteries are expected to promote the sustainable development of human civilization.     

Composition Modulation and Structure Design of Inorganic‐in‐Polymer Composite Solid Electrolytes for Advanced Lithium Batteries

Owing to their safety, high energy density, and long cycling life, all‐solid‐state lithium batteries (ASSLBs) have been identified as promising systems to power portable electronic devices and electric vehicles. Developing high‐performance solid‐state electrolytes is vital for the successful commercialization of ASSLBs. In particular, polymer‐based composite solid electrolytes (PCSEs), derived from the incorporation of inorganic fillers into polymer solid electrolytes, have emerged as one of the most promising electrolyte candidates for ASSLBs because they can synergistically integrate many merits from their components. The development of PCSEs is summarized. Their major components, including typical polymer matrices and diverse inorganic fillers, are reviewed in detail. The effects of fillers on their ionic conductivity, mechanical strength, thermal/interfacial stability and possible Li⁺‐conductive mechanisms are discussed. Recent progress in a number of rationally constructed PCSEs by compositional and structural modulation based on different design concepts is introduced. Successful applications of PCSEs in various lithium‐battery systems including lithium–sulfur and lithium–gas batteries are evaluated. Finally, the challenges and future perspectives for developing high‐performance PCSEs are proposed.     

An Overview of Fiber-Shaped Batteries with a Focus on Multifunctionality,Scalability, and Technical Difficulties

Flexible and wearable energy storage devices are receiving increasing attention with the ever-growing market of wearable electronics. Fiber-shaped batteries display a unique 1D architecture with the merits of superior flexibility, miniaturization potential, adaptability to deformation, and compatibility with the traditional textile industry, which are especially advantageous for wearable applications. In the recent research frontier in the field of fiber-shaped batteries, in addition to higher performance, advances in multifunctional, scalable, and integrable systems are also the main themes. However, many difficulties exist, including difficult encapsulation and installation of separators, high internal resistance, and poor durability. Herein, the design principles (e.g., electrode preparation and battery assembly) and device performance (e.g., electrochemical and mechanical properties) of fiber-shaped batteries, including lithium-based batteries, zinc-based batteries, and some other representative systems, are summarized, with a focus on multifunctional devices with environmental adaptability, stimuli-responsive properties, and scalability up to energy textiles, with the hope of enlightening future research directions. Finally, technical challenges in the realistic wearable application of these batteries are also discussed with the aim of providing possible solutions and new insights for further improvement.     

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。     

Customizable solid-state batteries toward shape-conformal and structural power supplies

With the advent of intelligent electronics and green transportation systems, power sources with customized shape, flexibility, functionality and high security are indispensable. Innovative customizable solid-state batteries have recently been explored as a key-enabling technology to achieve this vision. Such custom-made power sources enable the monolithic integration of bipolar-stacked cells onto complex-shaped substrates, maximize space utilization of devices, meanwhile minimize the use of inactive components. Hence, they hold great potential in reducing the total weight of target electronic devices, extending their lifespan, and even as structural batteries to replace structural components in robotics, implants and electric vehicles. This review describes state-of-the-art of customizable solid-state batteries with a focus on fabrication techniques and corresponding material considerations. The relationship between the battery architecture design and form-factors of cells concerning their mechanical and electrochemical properties are in focus. The challenges and future developments of customizable solid-state batteries are elaborated with respect to their potential applications. Through novel material engineering, structural evolution, on-going extension of high-throughput fabrication technology, and integration of multifunctional systems, the customizable solid-state batteries will pave their way to power a growing share of smart electronics and modern transportation systems.