Electrolytic alloy-type anodes for metal-ion batteries

Alloy-type metals/alloys hold the promise of increasing the energy density of metal-ion batteries(MIBs)because of their theoretical high gravimetrical capacities.Semimetals and semimetal-analogs are typical alloy-type anodes.Currently,the large-scale extraction of semimetals(Si,Ge) and semimetal-analogs(Sb,Bi,Sn) by traditional metallurgical routes highly relies on using reducing agents(e.g.,carbon,hydrogen,reactive metals),which consumes a large number of fossil fuels and produces greenhouse gas emissions.In addition,the common metallurgical methods for extracting semimetals involve relatively high operating temperatures and therefore produce bulk metal ingots solidified from the liquid metals.However,the commonly used electrode materials in batteries are fine powders.Thus,directly producing semimetal powders would be more energy efficient.In addition,semimetals are good candidates to host alkali/alkaline-earth ions through the alloying process because the electronegativity of semimetals is high.Therefore,preparing semimetal powders via an environment-sound manner is of great interest to provide sustainable anode materials for MIBs while reducing the ecological footprint.Low-cost and high-output capacity anode powder materials,as well as straightforward and environmental-benign synthetic methods,play key roles in enabling the energy conversion and storage technologies for real applications of MIBs.Electrochemical technologies offer new strategies to extract semimetals using electrons as the reducing agent that comes from renewable energies.Besides,the morphologies and structures of the electrolytic products can be rationally tailored by tuning the electrode potentials,electrolytes,and operating temperatures.In this regard,using the one-step green electrochemical method to prepare high-capacity and cheaper alloy-type metalloids for MIB anodes can fulfill the requirements for developing MIBs.This review critically overviews recent developments and advances in the electrochemical extraction of semimetals(Si,Ge) and semimetal-analogs(Sb,Bi,Sn) for MIBs,including basic electrochemical principles,thermodynamic analysis,manufacture strategies and applications in lithium-ion batteries(LIBs),sodium-ion batteries(SIBs),potassium-ion batteries(PIBs),magnesium-ion batteries(Mg-ion batteries),and liquid metal batteries(LMBs).It also presents challenges and prospects of employing electrochemical approaches for preparing alloy-type anode materials directly from inexpensive ore-originated feedstocks.     

Antimony-based intermetallic compounds for lithium-ion and sodium-ion batteries: synthesis,construction and application

The development of alternative electrode materials with high energy densities and power densities for batteries has been actively pursued to satisfy the power demands for electronic devices and hybrid electric vehicles. Recently, antimony(Sb)-based intermetallic compounds have attracted considerable research interests as new candidate anode materials for high-performance lithium-ion batteries(LIBs) and sodium-ion batteries(SIBs) due to their high theoretical capacity and suitable operating voltage. However, these intermetallic systems undergo large volume change during charge and discharge processes, which prohibits them from practical application. The rational construction of advanced anode with unique structures has been proved to be an effective approach to enhance its electrochemical performance. This review highlights the recent progress in improving and understanding the electrochemical performances of various Sb-based intermetallic compound anodes. The developments of synthesis and construction of Sb-based intermetallic compounds are systematically summarized. The electrochemical performances of various Sb-based intermetallic compound anodes are compared in its typical applications(LIBs or SIBs).     

锂离子电池硅基负极材料研究进展

本文主要介绍近年来硅及含硅材料作为锂离子电池负极材料的研究进展，包括硅单质、硅的氧化物以及硅的金属化合物和其它硅基多元化合物；分析了硅基材料作为锂离子电池负极材料存在的问题；阐述了硅基材料作为锂离子电池负极材料的研究前景。     

High-performance anode materials for Na-ion batteries

Na-ion batteries are considered a promising alternative to Li-ion batteries for large-scale energy storage systems due to their low cost and the natural abundance of Na resource. Great effort is making worldwide to develop high-performance electrode materials for Na-ion batteries,which is critical for Na-ion batteries. This review provides a comprehensive overview of anode materials for Na-ion batteries based on Na-storage mechanism: insertion-based materials, alloy-based materials, conversion-based materials and organic composites. And we summarize the Nastorage mechanism of those anode materials and discuss their failure mechanism. Furthermore, the problems and challenges associated with those anodes are pointed out,and feasible strategies are proposed for designing highperformance anode materials. According to the current state of research, the search for suitable anode materials for Na-ion batteries is still challenging although substantial progress has been achieved. Nevertheless, we believe that high-performance Na-ion batteries would be promising for practical applications in large-scale energy storage systems in the near future.     

金属有机框架衍生的Bi/C复合材料作为钠离子电池负极材料的研究

金属铋(Bi)用作钠离子电池的负极材料具有较高的理论比容量和较低的嵌钠电位,但是在钠离子嵌入和脱出的过程中容易发生较为严重的体积膨胀,从而导致循环性能较差。为改善金属Bi负极的循环性能,将其与具有多孔结构的碳复合是一种有效的改善手段。在过去几年中,金属有机框架(metal-organic frameworks,MOFs)作为一种合成前驱体被广泛应用于各种金属氧化物及多孔碳材料的合成中。合成了一种含铋的金属有机框架材料,并以其为前驱体,再经高温煅烧合成了多孔碳包覆的金属铋复合材料,该复合材料中的碳骨架及其丰富的孔结构能有效缓解Bi在钠离子脱嵌过程中的体积膨胀,从而提高其循环稳定性。     

硅基锂离子电池负极材料研究进展

作为锂离子电池负极材料,硅基材料具有较高的理论比容量、适中的嵌/脱锂电位、与电解液反应活性低等特点,成为最有前景的锂离子电池负极材料之一。然而由于其巨大的体积效应和较低的导电性导致其商业化应用具有相当的挑战性。本文综述了近年来为改善硅基材料的缺点而做的一些研究,展望了硅基材料作为锂离子电池负极材料的发展趋势。     

A Review of Metal Silicides for Lithium-Ion Battery Anode Application

Lithium batteries(LIBs) with low capacity graphite anode(～372 mAh g~(-1)) cannot meet the ever-growing demand for new energy electric vehicles and renewable energy storage.It is essential to replace graphite anode with higher capacity anode materials for high-energy density LIBs.Silicon(Si) is well known to be a possible alternative for graphite anode due to its highest capacity(～4200 mAh g~(-1)).Unfortunately,large volume change during lithiation and delithiation has prevented the Si anode from being commercialized.Metal silicides are a promising type of anode materials which can improve cycling stability via the accommodation of volume change by dispersing Si in the metal inactive/active matrix,while maintain greater capacity than graphite.Here,we present a classification of Si alloying with metals in periodic table of elements,review the available literature on metal silicide anodes to outline the progress in improving and understanding the electrochemical performance of various metal silicides,analyze the challenges that remain in using metal silicides,and offer perspectives regarding their future research and development as anode materials for commercial LIBs application.     

海水电池用镁合金阳极的研究进展

海水电池用镁合金阳极因其较负的电极电位、低的质量密度、大的电化学当量而受到人们的广泛关注.概述了近年来有关海水电池用镁合金的研究进展.首先,介绍了常见镁合金海水电池的分类(镁/金属氯化物电池、镁/海水溶解氧电池、镁/过氧化氢半燃料电池),详细说明了几种电池的工作条件与应用领域.其次,归纳了镁合金海水电池存在的问题,包括...     

Recent progress in cobalt-based compounds as high-performance anode materials for lithium ion batteries

Despite carbonaceous materials are widely employed as commercial negative electrodes for lithium ion battery, an urge requirement for new electrode materials that meet the needs of high energy density, long cycle life, low cost and safety is still underway. A number of cobalt-based compounds(Co(OH)_2, Co_3O_4, CoN, CoS,CoP, NiCo_2O_4, etc.) have been developed over the past years as promising anode materials for lithium ion batteries(LIBs) due to their high theoretical capacity, rich redox reaction and adequate cyclability. The LIBs performances of the cobalt-based compounds have been significantly improved in recent years, and it is anticipated that these materials will become a tangible reality for practical applications in the near future. However, the different types of cobalt-based compounds will result in diverse electrochemical performance. This review briefly analyzes recent progress in this field, especially highlights the synthetic approaches and the prepared nanostructures of the diverse cobalt-based compounds and their corresponding performances in LIBs, including the storage capacity, rate capability, cycling stability and so on.     

锂离子电池锑基负极材料研究进展

锑具有首次嵌／脱锂容量大等优点，是制备大容量高安全性锂离子电池负极潜在的优良材料。本文介绍了此系列材料的制备方法、特性及其用途。     

Alloy anodes for sodium-ion batteries

Sodium-ion batteries(SIBs) have emerged as one of the most promising candidates for next-generation energy storage systems because sodium is abundant in nature.The practical application of SIBs critically depends on developing robust electrode materials with high specific capacity and long cycling life,developing suitable anode materials is even more challenging.Alloy-type anodes are attractive for their high gravimetric and volumetric specific capacities,demonstrating great potential for high-energy SIBs,however,huge volume swelling hampered their practical application.Given the encouraging breakthroughs on alloy anodes for SIBs,herein,we present a review of the up-to-date progress and works carried out with alloy-based anode materials for SIBs.We review the synthetic strategies and their detailed electrochemical performance.In particular,we extensively reveal the important roles of alloy-based anodes in the development of SIBs.Research progress of alloy-type anodes and their compounds for sodium storage is summarized.Specific efforts to enhance the electrochemical performance of the alloy-based anode materials are discussed.Finally,we proposed multi-component alloys/high-entropy alloys(HEAs) as further research directions for alloy-based anodes.     

Comparison of Additives in Anode:The Case of Graphene,MXene,CNTs Integration with Silicon Inside Carbon Nanofibers

Recently,graphene oxide(GO),MXene,carbon nanotubes(CNTs) have been used for compounding with other materials as anodes and cathodes to achieve excellent electrochemical properties for metal-ion batteries.However,few researches have focused on the differences between the three additives.Herein,silicon,as a typical anode,is selected to integrate with MXene,GO and CNTs in carbon nanofibers(CNFs) and form Si/MXene@CNFs,Si/GO@CNFs and Si/CNTs@CNFs,respectively.Together with the results,it can be realized that these CNFs with a significant improved performance compared with pure Si@CNFs show superiority in different aspects of electrochemical properties.Additionally,the reasons for the superiority are also discussed in this work.The addition of MXene can improve the cycle stability of the electrodes,thereby obtaining a high capacity retention rate,CNTs are favorable for the enhancement of rate performance,and the electrodes reversible capacity can be increased due to the addition of GO.Consequently,the studies on three additives may contribute to the rational design of silicon-based and other anode materials.     

锂离子电池用石墨负极材料改性研究进展

石墨是目前商业化锂离子电池应用最广的负极材料,日益增长的市场需求对石墨负极材料的储锂性能提出了更高的要求。概述了锂离子电池的工作原理和石墨嵌锂机制,针对石墨负极材料理论比容量(372 mA.h/g)较低和电解液兼容性较差等问题,总结了近年来石墨负极材料的改性手段,主要分为表面改性和结构调控等2类,其中表面改性技术包括氧化和卤化处理,特点是通过调控界面化学性质,可增强石墨结构的稳定性,促进稳定SEI膜的形成,但对于石墨储锂容量的提升非常有限;结构调控包括剥层法和缺陷构筑法,特点是通过扩大石墨层间距、降低石墨维度及在石墨结构上构筑缺陷,从而增加锂离子的活性位点,提供更多锂离子扩散通道,缓解循环过程中的体积变化,改善石墨与电解液的相容性,显著提升石墨的储锂性能。最后对石墨负极材料的未来发展趋势进行了展望。     

Facile Preparation of NiO@graphene Nanocomposite with Superior Performances as Anode for Li-ion Batteries

Transition metal oxides gain considerable research attentions as potential anode materials for lithium ion batteries, but their applications are hindered due to their poor electronic conductivity, weak cycle stability and drastic volume change. Here, a NiO@graphene composite with a unique 3D conductive network structure is prepared through a simple strategy. When applied as anode material for Li-ion batteries, at 50 mA g^-1, the NiO@graphene displays a high reversible capacity of 1366 mAh g^-1 and a stable cyclability of 205 mAh g^-1 after 500 cycles. Even at a high rate of 10 A g^-1, it displays a favorable reversible capacity of 711 mAh g^-1. Remarkably, when it recovers back to 0.05 A g^-1, a reversible capacity of 1741 mAh g^-1 is achieved. Thus, the NiO@graphene composite with 3D structure shows good application prospects as an alternative anode for advanced lithium ion batteries.     

锗基锂离子电池负极材料的制备及研究进展

随着便携式电子产品及电动汽车的快速发展,提高锂离子电池能量密度和功率密度的研究日益增多,其中负极材料作为锂离子电池必备部件之一已成为重要的研究方向。商用的石墨负极因理论容量较低限制了其应用,锗具有较高的理论比容量和优异的物理化学性质,成为锂离子电池负极材料的研究热点。本文介绍了不同形貌和组成的锗基纳米负极材料的制备方法以及国内外的研究进展,并对未来的发展方向进行了展望。     

Sodium-beta alumina batteries: Status and challenges

This paper provides a review of materials and designs for sodium-beta alumina battery technology and discusses the challenges ahead for further technology improvement. Sodium-beta alumina batteries have been extensively developed in recent years and encouraging progress in performance and cycle life has been achieved. The battery is composed of an anode, typically molten sodium, and a cathode that can be molten sulfur (Na-S battery) or a transition metal halide incorporated with a liquid phase secondary electrolyte (e.g., ZEBRA battery). In most cases the electrolyte is a dense solid β″-Al₂O₃ sodium ion-conducting membrane. The issues prohibiting widespread commercialization of sodium-beta alumina technology are related to the materials and methods of manufacturing that impact cost, safety, and performance characteristics.     

贵金属阳极材料的应用与研究进展

贵金属阳极材料具有优异的电催化性能,为提高其催化活性,节能减耗减少其用量人们做了大量的研究。基于近十年来50余篇文献的分析,本文综述了贵金属阳极材料在基础化学工业的广泛应用及研究现状。展示了不同贵金属阳极的特点、发展历程和应用领域。介绍了贵金属氧化物阳极在电解水、氯碱工业、工业催化和废水处理等方面的应用进展,讨论了阳极材料的载体、控制形状、组成与物理化学特征之间的关系。对贵金属阳极材料的进一步发展及合理设计进行了展望。     

锂离子电池的工作原理与关键材料

锂离子电池具有能量密度高、自放电小和循环寿命长等优点,被广泛用于便携式电子设备和电动汽车等方面,不断推动着社会朝着智能化和清洁化方向发展.简要阐述了锂离子电池的发展历程和工作原理,从材料结构和储锂机制方面对正极材料和负极材料进行分类并综述其性能特点与研究现状,介绍了液态电解液中锂盐、溶剂、添加剂以及固态电解质在锂离子电...     

A Review of Al Alloy Anodes for Al-Air Batteries in Neutral and Alkaline Aqueous Electrolytes

Aluminum-air(Al-air) batteries are promising candidates for energy storage applications because of their high theoretical energy density and low cost.Nevertheless,their developments have been severely hindered by multiple obstacles,among which the activation and self-corrosion inhibition of Al anode have been considered to be significant challenges.In neutral electrolytes,the main problem is the activation of Al anode,while the self-corrosion of Al anode becomes dominant in alkaline electrolytes.Considerable efforts have been devoted to overcoming the dilemma associated with the Al anode.This review firstly underscores the underlying mechanisms of passivation and self-corrosion of Al anode in different electrolytes.Then,specific attentions are paid to Al alloy anode,including the role of various elements and standard processing technology.Finally,general conclusions,current limitations,and future perspectives on Al alloy anode are presented.     

Challenges and strategies for ultrafast aqueous zinc-ion batteries

With the rising demand for fast-charging technology in electric vehicles and portable devices,significant efforts have been devoted to the development of the highrate batteries.Among numerous candidates,rechargeable aqueous zinc-ion batteries(ZlBs) are a promising option due to its high theoretical capacity,low redox potential of zinc metal anode and inherent high ionic conductivity of aqueous electrolyte.As the strong electrostatic interaction between Zn~(2+) and host generally leads to sluggish electrode kinetics,many strategies have been proposed to enhance fast(dis)charging performance.Herein,we review the state-of-the-art ultrafast aqueous ZIBs and focus on the rational electrode-designing strategies,such as crystal structure engineering,nanostructuring and morphology controlling,conductive materials introducing and organic molecule designing.Recent research directions and future perspectives are also proposed in this review.