Defect Engineering on Electrode Materials for Rechargeable Batteries

The reasonable design of electrode materials for rechargeable batteries plays an important role in promoting the development of renewable energy technology. With the in-depth understanding of the mechanisms underlying electrode reactions and the rapid development of advanced technology, the performance of batteries has significantly been optimized through the introduction of defect engineering on electrode materials. A large number of coordination unsaturated sites can be exposed by defect construction in electrode materials, which play a crucial role in electrochemical reactions. Herein, recent advances regarding defect engineering in electrode materials for rechargeable batteries are systematically summarized, with a special focus on the application of metal-ion batteries, lithium–sulfur batteries, and metal–air batteries. The defects can not only effectively promote ion diffusion and charge transfer but also provide more storage/adsorption/active sites for guest ions and intermediate species, thus improving the performance of batteries. Moreover, the existing challenges and future development prospects are forecast, and the electrode materials are further optimized through defect engineering to promote the development of the battery industry.     

A Novel Aminoalkylsilane Compound with Oligo（ethylene oxide） Units as Effective Additive for Improving Cyclability of Lithium-ion Batteries

A new aminoalkylsilane compound, （（2-（2-（N,N-dimethylamino）ethoxy）ethoxy） methyl）trimethylsilane （TMSC1N2） based on the oligo（ethylene oxide） chain end-capped with organosilicon functional group and alkylamine group on each end, was introduced as an electrolyte additive for lithium-ion batteries. Electrochemical performances of different volume ratios of TMSC1N2 in the baseline electrolyte were conducted through cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/ discharge tests of lithium-ion batteries. With adding 5 vol.% TMSC1N2 to the baseline electrolyte （1 mol/L LiPF6 in ethylene carbonate and diethyl carbonate （EC：DEC = 1：1, in volume））, the capacity retention of LiFePO4/Li cells could be significantly improved from 74.7% to 90.8% after 130 cycles. Furthermore, TMSC1N2 showed good compatibility with graphite electrode and would not deteriorate the electrochemical performance of graphite/Li anode cells. These data suggested that TMSC1N2 could be utilized as an effective additive for lithium-ion batteries.     

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.     

Engineering Oxygen Vacancies in a Polysulfide-Blocking Layer with Enhanced Catalytic Ability

The practical application of the lithium–sulfur (Li–S) battery is seriously restricted by its shuttle effect, low conductivity, and low sulfur loading. Herein, first-principles calculations are conducted to verify that the introduction of oxygen vacancies in TiO₂ not only enhances polysulfide adsorption but also greatly improves the catalytic ability and both the ion and electron conductivities. A commercial polypropylene (PP) separator decorated with TiO₂ nanosheets with oxygen vacancies (OVs-TiO₂@PP) is fabricated as a strong polysulfide barrier for the Li–S battery. The thickness of the OVs-TiO₂ modification layer is only 500 nm with a low areal mass of around 0.12 mg cm⁻², which enhances the fast lithium-ion penetration and the high energy density of the whole cell. As a result, the cell with the OVs-TiO₂@PP separator exhibits a stable electrochemical behavior at 2.0 C over 500 cycles, even under a high sulfur loading of 7.1 mg cm⁻², and an areal capacity of 5.83 mAh cm⁻² remains after 100 cycles. The proposed strategy of engineering oxygen vacancies is expected to have wide applications in Li–S batteries.     

Recent Advances on Mixed Metal Sulfides for Advanced Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have drawn enormous attention in the past few years from both academic and industrial battery communities in view of the fascinating advantages of rich abundance and low cost of sodium resources. Among various electrode materials, mixed metal sulfides (MMSs) stand out as promising negative electrode materials for SIBs considering their superior structural and compositional advantages, such as decent electrochemical reversibility, high electronic conductivity, and rich redox reactions. Here, a summary of some recent developments in the rational design and synthesis of various kinds of MMSs with tailorable architectures, structural/compositional complexity, controllable morphologies, and enhanced electrochemical properties is presented. The effect of structural engineering and compositional design of MMSs on the sodium storage properties is highlighted. It is anticipated that further innovative works on the material design of advanced electrodes for batteries can be inspired.     

High-Safety and High-Energy-Density Lithium Metal Batteries in a Novel Ionic-Liquid Electrolyte

Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, lithium metal batteries in a novel nonflammable ionic-liquid (IL) electrolyte composed of 1-ethyl-3-methylimidazolium (EMIm) cations and high-concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite-free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to ≈16 mg cm⁻². Li anodes paired with lithium cobalt oxide (LiCoO₂) and lithium nickel cobalt manganese oxide (LiNi_0.8Co_0.1Mn_0.1O₂, NCM 811) cathodes exhibit 99.6–99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to ≈199 mAh g⁻¹ and ≈765 Wh kg⁻¹ respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li–NMC 811 full batteries.     

功能化离子液体在锂二次离子电池中的应用

离子液体由于具有热稳定性好、电导率高、质材料在不同电池体系中的应用成为当前研究的热点。面的阐述,并对其应用前景进行了展望。电化学窗口宽、不挥发、不燃烧等特点,其作为新一代功能化电解本文对功能化的离子液体在电池体系中的最新研究进展作了较为全     

Performance Evaluation of Composite Electrolyte with GQD for All-Solid-State Lithium Batteries

The use a stabilized lithium structure as cathode material for batteries could be a fundamental alternative in the development of next-generation energy storage devices. However, the lithium structure severely limits battery life causes safety concerns due to the growth of lithium (Li) dendrites during rapid charge/discharge cycles. Solid electrolytes, which are used in high-density energy storage devices and avoid the instability of liquid electrolytes, can be a promising alternative for next-generation batteries. Nevertheless, poor lithium ion conductivity and structural defects at room temperature have been pointed out as limitations. In this study, through the application of a low-dimensional graphene quantum dot (GQD) layer structure, stable operation characteristics were demonstrated based on Li⁺ ion conductivity and excellent electrochemical performance. Moreover, the device based on the modified graphene quantum dots (GQDs) in solid state exhibited retention properties of 95.3% for 100 cycles at 0.5 C and room temperature (RT). Transmission electron microscopy analysis was performed to elucidate the Li⁺ ion action mechanism in the modified GQD/electrolyte heterostructure. The low-dimensional structure of the GQD-based solid electrolyte has provided an important strategy for stably-scalable solid-state lithium battery applications at room temperature. It was demonstrated that lithiated graphene quantum dots (Li-GQDs) inhibit the growth of Li dendrites by regulating the modified Li⁺ ion flux during charge/discharge cycling at current densities of 2.2–5.5 mA cm, acting as a modified Li diffusion heterointerface. A full Li GQD-based device was fabricated to demonstrate the practicality of the modified Li structure using the Li–GQD hetero-interface. This study indicates that the low-dimensional carbon structure in Li–GQDs can be an effective approach for stabilization of solid-state Li matrix architecture.     

Chemical Immobilization Effect on Lithium Polysulfides for Lithium–Sulfur Batteries

Despite great progress in lithium–sulfur batteries (LSBs), great obstacles still exist to achieve high loading content of sulfur and avoid the loss of active materials due to the dissolution of the intermediate polysulfide products in the electrolyte. Relationships between the intrinsic properties of nanostructured hosts and electrochemical performance of LSBs, especially, the chemical interaction effects on immobilizing polysulfides for LSB cathodes, are discussed in this Review. Moreover, the principle of rational microstructure design for LSB cathode materials with strong chemical interaction adsorbent effects on polysulfides, such as metallic compounds, metal particles, organic polymers, and heteroatom‐doped carbon, is mainly described. According to the chemical immobilizing mechanism of polysulfide on LSB cathodes, three kinds of chemical immobilizing effects, including the strong chemical affinity between polar host and polar polysulfides, the chemical bonding effect between sulfur and the special function groups/atoms, and the catalytic effect on electrochemical reaction kinetics, are thoroughly reviewed. To improve the electrochemical performance and long cycling life‐cycle stability of LSBs, possible solutions and strategies with respect to the rational design of the microstructure of LSB cathodes are comprehensively analyzed.     

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(2 600 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。     

MXene-Based Dendrite-Free Potassium Metal Batteries

Potassium metal batteries are considered as attractive alternatives beyond lithium-ion batteries. However, uncontrollable dendrite growth on the potassium metal anode has restrained their practical applications. A high-performance potassium anode achieved by confining potassium metal into a titanium-deficient nitrogen-containing MXene/carbon nanotube freestanding scaffold is reported. The high electronic transport and fast potassium diffusion in this scaffold enable reduced local current density and homogeneous ionic flux during plating/stripping processes. Furthermore, as verified by theoretical calculations and experimental investigations, such “potassium-philic” MXene sheets can induce the nucleation of potassium, and guide potassium to uniformly distribute in the scaffold upon cycling. Consequently, the as-developed potassium metal anodes exhibit a dendrite-free morphology with high Coulombic efficiency and long cycle life during plating/stripping processes. Such anodes also deliver significantly improved electrochemical performances in potassium–sulfur batteries compared with bare potassium metal anodes. This work can provide a new avenue for developing potassium metal-based batteries.     

Recent Advances in Fiber-Shaped Supercapacitors and Lithium-Ion Batteries

The rapid development in wearable electronics has spurred a great deal of interest in flexible energy storage devices, particularly fiber-shaped energy storage devices (FSESDs), such as fiber-shaped supercapacitors (FSSCs) and fiber-shaped batteries (FSBs). Depending on their electrode configurations, FSESDs can contain five differently structured electrodes, including parallel fiber electrodes (PFEs), twisted fiber electrodes (TFDs), wrapped fiber electrodes (WFEs), coaxial fiber devices (CFEs), and rolled electrodes (REs). Various rational methods have been devised to incorporate these fiber-shaped electrodes into multifunctional FSESDs, including fiber-shaped supercapacitors, lithium-ion batteries, lithium–sulfur batteries, lithium–air batteries, zinc–air batteries, and aluminum–air batteries. Although significant progress has been made in FSESDs, it remains a major challenge to make high-performance fiber-shaped devices at low cost. A focused and critical review of the recent advancements in fiber-shaped supercapacitors and lithium-ion batteries is provided here. The pros and cons for each of the aforementioned electrode configurations and FSESDs are discussed, along with current challenges and future opportunities for FSESDs.     

Recent Advances in Layered Ti3C2Tx MXene for Electrochemical Energy Storage

Ti₃C₂T_x, a typical representative among the emerging family of 2D layered transition metal carbides and/or nitrides referred to as MXenes, has exhibited multiple advantages including metallic conductivity, a plastic layer structure, small band gaps, and the hydrophilic nature of its functionalized surface. As a result, this 2D material is intensively investigated for application in the energy storage field. The composition, morphology and texture, surface chemistry, and structural configuration of Ti₃C₂T_x directly influence its electrochemical performance, e.g., the use of a well‐designed 2D Ti₃C₂T_x as a rechargeable battery anode has significantly enhanced battery performance by providing more chemically active interfaces, shortened ion‐diffusion lengths, and improved in‐plane carrier/charge‐transport kinetics. Some recent progresses of Ti₃C₂T_x MXene are achieved in energy storage. This Review summarizes recent advances in the synthesis and electrochemical energy storage applications of Ti₃C₂T_x MXene including supercapacitors, lithium‐ion batteries, sodium‐ion batteries, and lithium–sulfur batteries. The current opportunities and future challenges of Ti₃C₂T_x MXene are addressed for energy‐storage devices. This Review seeks to provide a rational and in‐depth understanding of the relation between the electrochemical performance and the nanostructural/chemical composition of Ti₃C₂T_x, which will promote the further development of 2D MXenes in energy‐storage applications.     

锂硫电池硫正极材料研究现状与展望

综述了锂硫电池硫正极材料的研究现状。针对锂硫电池目前存在的问题,展望了其发展趋势,并指出硫/有序多孔碳纳米复合材料对提升锂硫电池性能有重要研究价值;同时形成三维空间传导网络的导电添加剂和具有良好粘接性、导电性及电化学稳定性的粘结剂对锂硫电池性能提升也具有重要作用。     

锂离子电池正极材料LiNi-x-yCoxMnyO2的研究现状

正极材料对锂离子电池的性能和价格具有决定性的作用，对正极材料的研究一直是锂离子电池研究中的热点。主要对一类新型正极材料LiNi-x-yCoxMnyO2的国内外研究现状进行了综述，并比较了不同合成方法对其电化学性能的影响，最后对这类正极材料的研究给予了展望。     

Transition Metal on the Electrochemical Performances of Some Intermetallic Anodes for Lithium Ion Batteries

Some transition metal antimonides were prepared by levitation melting and subsequent ball-milling. The electrochemical behaviors of these materials as new candidate negative electrode materials in lithium ion secondary batteries were investigated. It was found that they exhibited significantly larger volumetric capacity than carbon-based materials. The formation and composition of solid electrolyte interface (SEI) film were characterized by electrochemical impedance spectroscopy (EIS) and Fourier transform infra-red (FTIR) spectroscopy.     

高能锂离子电池的研究进展

近年来,锂离子电池因其优异的性能,发展十分迅速,锂离子电池的优异性能与电极材料的制备工艺及选择等密切相关,本文系统介绍了锂离子电池的工作原理,正负极材料及电解质的研究进展,并对锂离子电池研究中出现的问题提解决的途径。     

锂硫电池硫/导电聚合物正极材料的研究进展

综述了锂硫电池硫/导电聚合物正极材料的研究进展。重点探讨了导电聚合物在硫基正极材料改性中的制备方法、结构设计,并对其中存在的问题进行了分析。最后对硫/导电聚合物正极材料的进一步发展及商业化应用进行了展望。