Nanostructured strategies towards boosting organic lithium-ion batteries

Pursuing material development for next-generation batteries,organic electrode materials have shown great potential for lithium-ion batteries.However,their widespread adopting is plagued by intrinsic problems such as poor electronic conductivity,high dissolution inside electrolytes and unstable chemical peculiarity.Recently,nanostructured-strategies promoted organic electrodes with exotic properties for enhancing electron and ion transport together with the stability during electrochemical process,have received increasing attention and have been extensive applied in boosting the organic lithium-ion based energy storage.In this review,we summarize the applications of nanostructures to improve the performance of both organic anodes and cathodes,including(i)nanoscale design of zero-dimensional organic electrode materials,(ii)strategies of one-dimensional nanostructured organic electrode materials,(iii)construction of two-dimensional nanosized organic composite electrodes,and(iv)three-dimensional exploration of nanosized organic electrodes.We hope to stimulate high-quality applied research on understanding and handling the relationship between the nanostructure and performance of organic lithium-ion batteries that might speed up the commercialization of organic lithium ion batteries.     

镁离子电池正极材料研究进展

镁离子电池(MIBs)因镁资源储量丰富、体积能量密度大、金属镁空气中相对稳定等优势,被认为是具有大规模储能应用潜力的电池体系。然而,镁离子较高的电荷密度和较强的溶剂化作用导致其在正极材料中的可逆脱嵌和固-液界面上的离子扩散相当缓慢,严重影响了MIBs的电化学性能。近年来,人们针对MIBs正极材料开展了大量工作,取得了一定进展,但是还存在不少问题。本文先从MIBs体系的特点出发,阐述其优势和目前所面临的主要挑战,然后从无机正极材料和有机正极材料两方面展开,梳理并总结了各类正极材料的局限性及其解决策略,对优化方法和材料性能间的相关性进行归纳和讨论,为今后进一步发展具有优异电化学性能的MIBs正极材料提供可能的参考。     

Emerging Lithiated Organic Cathode Materials for Lithium-Ion Full Batteries

Organic electrode materials have application potential in lithium batteries owing to their high capacity, abundant resources, and structural designability. However, most reported organic cathodes are at oxidized states (namely unlithiated compounds) and thus need to couple with Li-rich anodes. In contrast, lithiated organic cathode materials could act as a Li reservoir and match with Li-free anodes such as graphite, showing great promise for practical full-battery applications. Here we summarize the synthesis, stability, and battery applications of lithiated organic cathode materials, including synthetic methods, stability against O₂ and H₂O in air, and strategies to improve comprehensive electrochemical performance. Future research should be focused on new redox chemistries and the construction of full batteries with lithiated organic cathodes and commercial anodes under practical conditions. This Minireview will encourage more efforts on lithiated organic cathode materials and finally promote their commercialization.     

Sulfur‐Based Electrodes that Function via Multielectron Reactions for Room‐Temperature Sodium‐Ion Storage

Emerging rechargeable sodium‐ion storage systems—sodium‐ion and room‐temperature sodium–sulfur (RT‐NaS) batteries—are gaining extensive research interest as low‐cost options for large‐scale energy‐storage applications. Owing to their abundance, easy accessibility, and unique physical and chemical properties, sulfur‐based materials, in particular metal sulfides (MS_x) and elemental sulfur (S), are currently regarded as promising electrode candidates for Na‐storage technologies with high capacity and excellent redox reversibility based on multielectron conversion reactions. Here, we present current understanding of Na‐storage mechanisms of the S‐based electrode materials. Recent progress and strategies for improving electronic conductivity and tolerating volume variations of the MS_x anodes in Na‐ion batteries are reviewed. In addition, current advances on S cathodes in RT‐NaS batteries are presented. We outline a novel emerging concept of integrating MS_x electrocatalysts into conventional carbonaceous matrices as effective polarized S hosts in RT‐NaS batteries as well. This comprehensive progress report could provide guidance for research toward the development of S‐based materials for the future Na‐storage techniques.     

锂离子电池纳微结构电极材料系列研究

纳米储锂电极材料由于奇特的纳米效应与动力学优势,为锂离子电池的发展提供了新的机遇.本文介绍了锂离子电池电极材料的尺寸效应、形貌效应以及电极材料碳包覆的作用;并以作者的近期研究为主,着重讨论了几种"动力学稳定"的纳微结构电极材料和具有"三维混合导电网络"结构的高倍率电极材料.     

Towards High Performance Chemical Vapour Deposition V2O5 Cathodes for Batteries Employing Aqueous Media

The need for clean and efficient energy storage has become the center of attention due to the eminent global energy crisis and growing ecological concerns. A key component in this effort is the ultra-high performance battery, which will play a major role in the energy industry. To meet the demands in portable electronic devices, electric vehicles, and large-scale energy storage systems, it is necessary to prepare advanced batteries with high safety, fast charge ratios, and discharge capabilities at a low cost. Cathode materials play a significant role in determining the performance of batteries. Among the possible electrode materials is vanadium pentoxide, which will be discussed in this review, due to its low cost and high theoretical capacity. Additionally, aqueous electrolytes, which are environmentally safe, provide an alternative approach compared to organic media for safe, cost-effective, and scalable energy storage. In this review, we will reveal the industrial potential of competitive methods to grow cathodes with excellent stability and enhanced electrochemical performance in aqueous media and lay the foundation for the large-scale production of electrode materials.     

2020 roadmap on two-dimensional materials for energy storage and conversion

In this roadmap, two-dimensional materials including graphene, black phosporus, MXenes, covalent organic frameworks, oxides, chalcogenides, and others, are highlighted in energy storage and conversion.     

2020 roadmap on two-dimensional materials for energy storage and conversion

Energy storage and conversion have attained significant interest owing to its important applications that reduce CO₂ emission through employing green energy. Some promising technologies are included metal-air batteries, metal-sulfur batteries, metal-ion batteries, electrochemical capacitors, etc. Here, metal elements are involved with lithium, sodium, and magnesium. For these devices, electrode materials are of importance to obtain high performance. Two-dimensional (2D) materials are a large kind of layered structured materials with promising future as energy storage materials, which include graphene, black phosporus, MXenes, covalent organic frameworks (COFs), 2D oxides, 2D chalcogenides, and others. Great progress has been achieved to go ahead for 2D materials in energy storage and conversion. More researchers will join in this research field. Under the background, it has motivated us to contribute with a roadmap on ‘two-dimensional materials for energy storage and conversion.     

Design Strategies for Vanadium‐based Aqueous Zinc‐Ion Batteries

Aqueous zinc‐ion batteries (ZIBs) are considered promising energy storage devices for large‐scale energy storage systems as a consequence of their safety benefits and low cost. In recent years, various vanadium‐based compounds have been widely developed to serve as the cathodes of aqueous ZIBs because of their low cost and high theoretical capacity. Furthermore, different energy storage mechanisms are observed in ZIBs based on vanadium‐based cathodes. In this Minireview, we present a comprehensive overview of the energy storage mechanisms and structural features of various vanadium‐based cathodes in ZIBs. Furthermore, we discuss strategies for improving the electrochemical performance of vanadium‐based cathodes; including, insertion of metal ions, adjustment of structural water, selection of conductive additives, and optimization of electrolytes. Finally, this Minireview offers insight into potential future directions in the design of innovative vanadium‐based electrode materials.     

Redox-Bipolar Polyimide Two-Dimensional Covalent Organic Framework Cathodes for Durable Aluminium Batteries

Emerging rechargeable aluminium batteries (RABs) offer a sustainable option for next-generation energy storage technologies with low cost and exemplary safety. However, the development of RABs is restricted by the limited availability of high-performance cathode materials. Herein, we report two polyimide two-dimensional covalent organic frameworks (2D-COFs) cathodes with redox-bipolar capability in RAB. The optimal 2D-COF electrode achieves a high specific capacity of 132 mAh g⁻¹. Notably, the electrode presents long-term cycling stability (with a negligible ≈0.0007 % capacity decay per cycle), outperforming early reported organic RAB cathodes. 2D-COFs integrate n-type imide and p-type triazine active centres into the periodic porous polymer skeleton. With multiple characterizations, we elucidate the unique Faradaic reaction of the 2D-COF electrode, which involves AlCl²⁺ and AlCl₄⁻ dual-ions as charge carriers. This work paves the avenue toward novel organic cathodes in RABs.     

有机电极材料过渡态的研究进展

有机电极材料具有理论比容量大、结构可设计性强、加工使用过程环境友好等优点被广泛应用于二次电池的研究中。有机电极材料在氧化还原过程会产生具有不成对电子的自由基中间体,自由基中间体的稳定程度影响电极材料的电化学性能。通过改变材料的结构可以调控自由基中间体的稳定性,从而优化有机电极材料的电化学性能。本文对有机电极材料在电化学过程中产生的自由基中间体进行了分类介绍,阐明了材料结构、自由基中间体稳定性和电化学性能之间的关系。     

锂硫电池复合正极研究进展

锂硫电池因其超高的理论能量密度被视为极具前景的下一代电化学储能体系,其中高比容量的硫正极提供了锂硫电池的能量密度优势并直接决定了电池的实际性能。经过数十年的发展,最具前景的硫正极体系分别是硫碳复合（S/C）正极和硫化聚丙烯腈（SPAN）正极。本文系统综述了S/C正极和SPAN正极的最新研究进展。首先,简要介绍了两种正极的工作原理并进行了比较。S/C正极发生固-液-固多相转化反应,充放电表现为双平台特征。与之相比,SPAN正极发生固-固反应,充放电曲线为单平台。然后,对两种正极所面临的挑战和目前报道的优化策略进行了系统的分析与讨论。对于S/C正极,主要调控策略包括电极结构修饰、电催化剂设计与辅助氧化还原介体调控;对于SPAN正极,主要调控策略包括电极结构设计、电极形貌调控、杂原子掺杂和外源性氧化还原介体调控。最后,在电池尺度上对S/C正极和SPAN正极进行了综合比较,并对基于S/C正极和SPAN正极的锂硫电池在未来所面对的机遇与挑战进行了展望。     

The electrochemistry of activated carbonaceous materials: past, present, and future

Carbonaceous materials are widely used in electrochemistry. All allotropic forms of carbons??graphite, glassy carbon, amorphous carbon, fullerenes, nanotubes, and doped diamond??are used as important electrode materials in all fields of modern electrochemistry. Examples include graphite and amorphous carbons as anode materials in high-energy density rechargeable Li batteries, porous carbon electrodes in sensors and fuel cells, nano-amorphous carbon as a conducting agent in many kinds of composite electrodes (e.g., cathodes based on intercalation inorganic host materials for batteries), glassy carbon and doped diamond as stable robust and high stability electrode materials for all aspects of basic electrochemical studies, and more. Amorphous carbons can be activated to form very high specific surface area (yet stable) electrode materials which can be used for electrostatic energy storage and conversion [electrical double-layer capacitors (EDLC)] and separation techniques based on electro-adsorption, such as water desalination by capacitive de-ionization (CDI). Apart from the many practical aspects of activated carbon electrodes, there are many highly interesting and important basic aspects related to their study, including transport phenomena, molecular sieving behavior, correlation between electrochemical behavior and surface chemistry, and more. In this article, we review several important aspects related to these electrode materials, in a time perspective (past, present, and future), with the emphasis on their importance to EDLC devices and CDI processes.     

Recent advances in cathodes for all-solid-state lithium-sulfur batteries

Lithium-sulfur (Li-S) batteries have been regarded as the candidate for the next-generation energy storage system due to the high theoretical specific capacity (1675 mAh/g), energy density (2600 Wh/kg) and the abundance of elemental sulfur, but the application of Li-S batteries is impeded by a series of problems. Recently, all-solid-state Li-S batteries (ASSLSBs) have drawn great attention because many drawbacks such as safety issues caused by metallic lithium anodes and organic liquid electrolytes can be overcome through the use of solid-state electrolytes (SEs). However, not only the problems brought by sulfur cathodes still exist, but more trouble arouses from the interfaces between SEs and cathodes, hampering the practical application of ASSLSBs. Therefore, in order to deal with the problems, enormous endeavors have been done on ASSLSB cathodes during the past few decades, including engineering of cathode active materials, cathode host materials, cathode binder materials and cathode structures. In this review, the electrochemical mechanism and existing problems of ASSLSBs are briefly introduced. Subsequently, the strategies for developing cathode materials and designing cathode structures are presented. Then there follows a brief discussion of SE problems and expectations, and finally, the challenges and perspectives of ASSLSBs are summarized.     

Nonaqueous magnesium electrochemistry and its application in secondary batteries

A revolution in modern electronics has led to the miniaturization and evolution of many portable devices, such as cellular telephones and laptop computers, since the 1980s. This has led to an increasing demand for new and compatible energy storage technologies. Furthermore, a growing awareness of pollution issues has provided a strong impetus for the science and technology community to develop alternatives with ever-higher energy densities, with the ultimate goal of being able to propel electric vehicles. Magnesium's thermodynamic properties make this metal a natural candidate for utilization as an anode in high-energy-density, rechargeable battery systems. We report herein on the results of extensive studies on magnesium anodes and magnesium insertion electrodes in nonaqueous electrolyte solutions. Novel, rechargeable nonaqueous magnesium battery systems were developed based on the research. This work had two major challenges: one was to develop electrolyte solutions with especially high anodic stability in which magnesium anodes can function at a high level of cycling efficiency; the other was to develop a cathode that can reversibly intercalate Mg ions in these electrolyte systems. The new magnesium batteries consist of Mg metal anodes, an electrolyte with a general structure of Mg(AlX(3-n)R(n)R')(2) (R',R = alkyl groups, X = halide) in ethereal solutions (e.g., tetrahydrofuran, polyethers of the "glyme" family), and Chevrel phases of MgMo(3)S(4) stoichiometry as highly reversible cathodes. With their practical energy density expected to be >60 Wh/Kg, the battery systems can be cycled thousands of times with almost no capacity fading. The batteries are an environmentally friendly alternative to lead-acid and nickel-cadmium batteries and are composed of abundant, inexpensive, and nonpoisonous materials. The batteries are expected to provide superior results in large devices that require high-energy density, high cycle life, a high degree of safety, and low-cost components. Further developments in this field are in active progress.     

Cathodes for Aqueous Zn-Ion Batteries: Materials,Mechanisms, and Kinetics

As concerns about the safety of lithium-ions batteries (LIBs) increases, aqueous zinc-ion batteries (ZIBs) with a lower cost, higher safety, and higher co-efficiency have attracted more and more interest. However, finding suitable cathode materials is still an urgent problem in ZIBs. In recent years, a lot of significant works have been reported, including manganese-based cathodes, vanadium-based cathodes, Prussian blue analog-based materials, and sustainable quinone cathodes. In this review, some typical cathode materials are introduced. The detailed storage mechanisms and methods for improving the reaction kinetics of the zinc ions are summarized. Finally, the issues, challenges, and the research directions are provided.     

基于有机物电极的电化学能量存储与转化

由于高安全的特性,水系二次电池被认为是未来大型储能的有效解决方案之一. 然而,现有水系电池主要以含金属元素的无机化合物为电极活性材料,其在大型储能中的实际应用仍受到循环寿命、环境问题、原料成本或金属元素丰度的限制. 相较于无机电极材料,部分有机电极材料具有原料丰富、结构丰富、可持续及环境友好等优点. 此外,有机物材料分子内空间大,能够存储不同价态电荷,因此近年来被广泛关注. 本文综述了课题组近期在有机物电极方面的研究进展,内容聚焦含羰基有机物通过C=O/C-O-的可逆转化存储单价金属阳离子(Li⁺, Na⁺)、双价金属阳离子(Zn²⁺)、质子(H⁺)所涉及的电化学过程,及其在水系锂、钠离子电池、水系锌离子电池、质子电池以及分步电解水中的应用.     

关于水系锌离子电池中无氧钒基正极材料的综述

水系锌离子电池具有功率密度高、环境友好、安全性高、低成本和锌资源丰富等优点，被认为具有潜力成为下一代电化学储能系统。然而，正极材料较差的电化学性能制约了水系锌离子电池的未来发展。尽管氧化锰、氧化钒、普鲁士蓝类似物、有机材料等多种材料已被广泛研究，设计具有高性能的理想正极材料仍面临着巨大挑战。无氧钒基化合物由于具有高的电导率、大的层间距、低的离子扩散势垒和高的理论比容量，受到越来越多的关注。本文总结了无氧钒基化合物的研究进展，包括电极材料的设计、改善其电化学性能的有效途径以及复杂的储能机制，提出了无氧钒基化合物目前面临的挑战和未来的发展前景，为进一步制备新型高性能钒基正极材料提供指导。     

Effects of Conjugated Structure on the Magnesium Storage Performance of Dianhydrides

Inorganic cathodes of rechargeable Mg batteries suffer from limited selections, while organic materials provide more options. Herein, three conjugated dianhydrides, pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride and 3,4,9,10-perylenetetracarboxylic dianhydride are comparatively investigated to elucidate the effects of conjugated structure on the Mg²⁺ storage performances. It is observed that the reversible Mg²⁺ storage capacity is more dependent on the conjugated structure than carbonyl numbers. Ex-situ mechanism study illustrates that the extended conjugated structure delocalizes the electron density, hence enhancing carbonyl enolization and increasing the Mg²⁺ storage capacity. Furthermore, the largely conjugated structure buffers the charge density change during repeated magnesiation/demagnesiation resulting in better cyclability. Prominently, 3,4,9,10-perylenetetracarboxylic dianhydride shows a high Mg²⁺ storage capacity (160 mAh g⁻¹) and a good cycling stability (80 % capacity retention after 100 cycles) with the largest conjugated structure. This work provides a low-cost cathode for rechargeable Mg batteries that can be utilized for designing high-performance organic Mg battery cathodes.     

Design Strategies for High-Performance Aqueous Zn/Organic Batteries

Organic electroactive compounds are attractive to serve as the cathode materials of aqueous zinc-ion batteries (ZIBs) because of their resource renewability, environmentally friendliness and structural diversity. Up to now, various organic electrode materials have been developed and different redox mechanisms are observed in aqueous Zn/organic battery systems. In this Minireview, we present the recent developments in the energy storage mechanisms and design of the organic electrode materials of aqueous ZIBs, including carbonyl compounds, imine compounds, conductive polymers, nitronyl nitroxides, organosulfur polymers and triphenylamine derivatives. Furthermore, we highlight the design strategies to improve their electrochemical performance in the aspects of specific capacity, output voltage, cycle life and rate capability. Finally, we discuss the challenges and future perspectives of aqueous Zn/organic batteries.