Novel 2D Layered Molybdenum Ditelluride Encapsulated in Few‐Layer Graphene as High‐Performance Anode for Lithium‐Ion Batteries

Molybdenum ditelluride nanosheets encapsulated in few‐layer graphene (MoTe₂/FLG) are synthesized by a simple heating method using Te and Mo powder and subsequent ball milling with graphite. The as‐prepared MoTe₂/FLG nanocomposites as anode materials for lithium‐ion batteries exhibit excellent electrochemical performance with a highly reversible capacity of 596.5 mAh g^?1 at 100 mA g^?1, a high rate capability (334.5 mAh g^?1 at 2 A g^?1), and superior cycling stability (capacity retention of 99.5% over 400 cycles at 0.5 A g^?1). Ex situ X‐ray diffraction and transmission electron microscopy are used to explore the lithium storage mechanism of MoTe₂. Moreover, the electrochemical performance of a MoTe₂/FLG//0.35Li₂MnO₃·0.65LiMn_0.5Ni_0.5O₂ full cell is investigated, which displays a reversible capacity of 499 mAh g^?1 (based on the MoTe₂/FLG mass) at 100 mA g^?1 and a capacity retention of 78% over 50 cycles, suggesting the promising application of MoTe₂/FLG for lithium‐ion storage. First‐principles calculations exhibit that the lowest diffusion barrier (0.18 eV) for lithium ions along pathway III in the MoTe₂ layered structure is beneficial for improving the Li intercalation/deintercalation property.     

Nanoscale Engineering of Heterostructured Anode Materials for Boosting Lithium‐Ion Storage

Rechargeable lithium‐ion batteries (LIBs), as one of the most important electrochemical energy‐storage devices, currently provide the dominant power source for a range of devices, including portable electronic devices and electric vehicles, due to their high energy and power densities. The interest in exploring new electrode materials for LIBs has been drastically increasing due to the surging demands for clean energy. However, the challenging issues essential to the development of electrode materials are their low lithium capacity, poor rate ability, and low cycling stability, which strongly limit their practical applications. Recent remarkable advances in material science and nanotechnology enable rational design of heterostructured nanomaterials with optimized composition and fine nanostructure, providing new opportunities for enhancing electrochemical performance. Here, the progress as to how to design new types of heterostructured anode materials for enhancing LIBs is reviewed, in the terms of capacity, rate ability, and cycling stability: i) carbon‐nanomaterials‐supported heterostructured anode materials; ii) conducting‐polymer‐coated electrode materials; iii) inorganic transition‐metal compounds with core@shell structures; and iv) combined strategies to novel heterostructures. By applying different strategies, nanoscale heterostructured anode materials with reduced size, large surfaces area, enhanced electronic conductivity, structural stability, and fast electron and ion transport, are explored for boosting LIBs in terms of high capacity, long cycling lifespan, and high rate durability. Finally, the challenges and perspectives of future materials design for high‐performance LIB anodes are considered. The strategies discussed here not only provide promising electrode materials for energy storage, but also offer opportunities in being extended for making a variety of novel heterostructured nanomaterials for practical renewable energy applications.     

Nanoparticle Cookies Derived from Metal‐Organic Frameworks: Controlled Synthesis and Application in Anode Materials for Lithium‐Ion Batteries

The capacity of anode materials plays a critical role in the performance of lithium‐ion batteries. Using the nanocrystals of oxygen‐free metal‐organic framework ZIF‐67 as precursor, a one‐step calcination approach toward the controlled synthesis of CoO nanoparticle cookies with excellent anodic performances is developed in this work. The CoO nanoparticle cookies feature highly porous structure composed of small CoO nanoparticles (≈12 nm in diameter) and nitrogen‐rich graphitic carbon matrix (≈18 at% in nitrogen content). Benefiting from such unique structure, the CoO nanoparticle cookies are capable of delivering superior specific capacity and cycling stability (1383 mA h g^?1 after 200 runs at 100 mA g^?1) over those of CoO and graphite.     

Novel Carbon‐Encapsulated Porous SnO2 Anode for Lithium‐Ion Batteries with Much Improved Cyclic Stability

Porous SnO₂ submicrocubes (SMCs) are synthesized by annealing and HNO₃ etching of CoSn(OH)₆ SMCs. Bare SnO₂ SMCs, as well as bare commercial SnO₂ nanoparticles (NPs), show very high initial discharge capacity when used as anode material for lithium‐ion batteries. However, during the following cycles most of the Li ions previously inserted cannot be extracted, resulting in considerable irreversibility. Porous SnO₂ cubes have been proven to possess better electrochemical performance than the dense nanoparticles. After being encapsulated by carbon shell, the obtained yolk–shell SnO₂ SMCs@C exhibits significantly enhanced reversibility for lithium‐ions storage. The reversibility of the conversion between SnO₂ and Sn, which is largely responsible for the enhanced capacity, has been discussed. The porous SnO₂ SMCs@C shows much increased capacity and cycling stability, demonstrating that the porous SnO₂ core is essential for better lithium‐ion storage performance. The strategy introduced in this paper can be used as a versatile way to fabrication of various metal‐oxide‐based composites.     

Reactive Oxygen‐Doped 3D Interdigital Carbonaceous Materials for Li and Na Ion Batteries

Carbonaceous materials as anodes usually exhibit low capacity for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). Oxygen‐doped carbonaceous materials have the potential of high capacity and super rate performance. However, up to now, the reported oxygen‐doped carbonaceous materials usually exhibit inferior electrochemical performance. To overcome this problem, a high reactive oxygen‐doped 3D interdigital porous carbonaceous material is designed and synthesized through epitaxial growth method and used as anodes for LIBs and SIBs. It delivers high reversible capacity, super rate performance, and long cycling stability (473 mA h g^?1after 500 cycles for LIBs and 223 mA h g^?1 after 1200 cycles for SIBs, respectively, at the current density of 1000 mA g^?1), with a capacity decay of 0.0214% per cycle for LIBs and 0.0155% per cycle for SIBs. The results demonstrate that constructing 3D interdigital porous structure with reactive oxygen functional groups can significantly enhance the electrochemical performance of oxygen‐doped carbonaceous material.     

Low‐Temperature Growth of All‐Carbon Graphdiyne on a Silicon Anode for High‐Performance Lithium‐Ion Batteries

In situ weaving an all‐carbon graphdiyne coat on a silicon anode is scalably realized under ultralow temperature (25 °C). This economical strategy not only constructs 3D all‐carbon mechanical and conductive networks with reasonable voids for the silicon anode at one time but also simultaneously forms a robust interfacial contact among the electrode components. The intractable problems of the disintegrations in the mechanical and conductive networks and the interfacial contact caused by repeated volume variations during cycling are effectively restrained. The as‐prepared electrode demostrates the advantages of silicon regarding capacity (4122 mA h g^?1 at 0.2 A g^?1) with robust capacity retention (1503 mA h g^?1) after 1450 cycles at 2 A g^?1, and a commercial‐level areal capacity up to 4.72 mA h cm^?2 can be readily approached. Furthermore, this method shows great promises in solving the key problems in other high‐energy‐density anodes.     

The Promise and Challenge of Phosphorus‐Based Composites as Anode Materials for Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are a core energy storage device that can meet the need for scalable and affordable stationary applications because they use low‐cost and earth‐abundant potassium. In addition, KIB shares a similar storage mechanism with current Li‐ion batteries. As the key to optimizing a battery's performance, the development of high‐performance electrode materials helps to increase the feasibility of KIB technology. In this sense, phosphorus‐based materials (i.e., phosphorus and metal phosphide) with high theoretical capacity and low redox potential tick all the right boxes as a material of choice. A rapid glimpse at recent studies on phosphorus‐based anode materials for advanced KIBs is provided, covering the synthetic methods, reaction mechanisms, electrochemical properties, and performances. In addition, several promising strategies are highlighted to address the imminent challenges faced by phosphorus‐based anode materials, hoping to cast an insightful outlook for possible future direction in this field.     

Scalable 2D Mesoporous Silicon Nanosheets for High‐Performance Lithium‐Ion Battery Anode

Constructing unique mesoporous 2D Si nanostructures to shorten the lithium‐ion diffusion pathway, facilitate interfacial charge transfer, and enlarge the electrode–electrolyte interface offers exciting opportunities in future high‐performance lithium‐ion batteries. However, simultaneous realization of 2D and mesoporous structures for Si material is quite difficult due to its non‐van der Waals structure. Here, the coexistence of both mesoporous and 2D ultrathin nanosheets in the Si anodes and considerably high surface area (381.6 m² g^?1) are successfully achieved by a scalable and cost‐efficient method. After being encapsulated with the homogeneous carbon layer, the Si/C nanocomposite anodes achieve outstanding reversible capacity, high cycle stability, and excellent rate capability. In particular, the reversible capacity reaches 1072.2 mA h g^?1 at 4 A g^?1 even after 500 cycles. The obvious enhancements can be attributed to the synergistic effect between the unique 2D mesoporous nanostructure and carbon capsulation. Furthermore, full‐cell evaluations indicate that the unique Si/C nanostructures have a great potential in the next‐generation lithium‐ion battery. These findings not only greatly improve the electrochemical performances of Si anode, but also shine some light on designing the unique nanomaterials for various energy devices.     

锂离子电池负极材料二氧化锡的研究进展

作为一种新型锂离子电池负极材料,二氧化锡由于具有高比容量、低嵌锂电势等优点而受到了广泛关注。但是二氧化锡在充放电循环中体积变化过大,导致其不可逆容量损失大、循环性能较差。纳米化和合金化是解决这一问题的有效途径。综述了纳米结构二氧化锡及其复合材料,特别是二氧化锡纳米线、纳米棒、纳米管、纳米片等与无定形碳、碳纳米管、石墨烯的复合材料在锂离子电池负极材料中的研究进展,并展望了其应用前景。     

SnO2‐Based Nanomaterials: Synthesis and Application in Lithium‐Ion Batteries

The development of new electrode materials for lithium‐ion batteries (LIBs) has always been a focal area of materials science, as the current technology may not be able to meet the high energy demands for electronic devices with better performance. Among all the metal oxides, tin dioxide (SnO₂) is regarded as a promising candidate to serve as the anode material for LIBs due to its high theoretical capacity. Here, a thorough survey is provided of the synthesis of SnO₂‐based nanomaterials with various structures and chemical compositions, and their application as negative electrodes for LIBs. It covers SnO₂ with different morphologies ranging from 1D nanorods/nanowires/nanotubes, to 2D nanosheets, to 3D hollow nanostructures. Nanocomposites consisting of SnO₂ and different carbonaceous supports, e.g., amorphous carbon, carbon nanotubes, graphene, are also investigated. The use of Sn‐based nanomaterials as the anode material for LIBs will be briefly discussed as well. The aim of this review is to provide an in‐depth and rational understanding such that the electrochemical properties of SnO₂‐based anodes can be effectively enhanced by making proper nanostructures with optimized chemical composition. By focusing on SnO₂, the hope is that such concepts and strategies can be extended to other potential metal oxides, such as titanium dioxide or iron oxides, thus shedding some light on the future development of high‐performance metal‐oxide based negative electrodes for LIBs.     

Ti‐Based Oxide Anode Materials for Advanced Electrochemical Energy Storage: Lithium/Sodium Ion Batteries and Hybrid Pseudocapacitors

Titanium‐based oxides including TiO₂ and M‐Ti‐O compounds (M = Li, Nb, Na, etc.) family, exhibit advantageous structural dynamics (2D ion diffusion path, open and stable structure for ion accommodations) for practical applications in energy storage systems, such as lithium‐ion batteries, sodium‐ion batteries, and hybrid pseudocapacitors. Further, Ti‐based oxides show high operating voltage relative to the deposition of alkali metal, ensuring full safety by avoiding the formation of lithium and sodium dendrites. On the other hand, high working potential prevents the decomposition of electrolyte, delivering excellent rate capability through the unique pseudocapacitive kinetics. Nevertheless, the intrinsic poor electrical conductivity and reaction dynamics limit further applications in energy storage devices. Recently, various work and in‐depth understanding on the morphologies control, surface engineering, bulk‐phase doping of Ti‐based oxides, have been promoted to overcome these issues. Inspired by that, in this review, the authors summarize the fundamental issues, challenges and advances of Ti‐based oxides in the applications of advanced electrochemical energy storage. Particularly, the authors focus on the progresses on the working mechanism and device applications from lithium‐ion batteries to sodium‐ion batteries, and then the hybrid pseudocapacitors. In addition, future perspectives for fundamental research and practical applications are discussed.     

Lamellarly Stacking Porous N,P Co‐Doped Mo2C/C Nanosheets as High Performance Anode for Lithium‐Ion Batteries

Layered stacking and highly porous N, P co‐doped Mo₂C/C nanosheets are prepared from a stable Mo‐enhanced hydrogel. The hydrogel is formed through the ultrafast cross‐linking of phosphomolybdic acid and chitosan. During the reduction of the composite hydrogel framework under inert gas protection, highly porous N and P co‐doped carbon nanosheets are produced with the in situ formation of ultrafine Mo₂C nanoparticles highly distributed throughout the nanosheets which are entangled via a hierarchical lamellar infrastructure. This unique architecture of the N, P co‐doped Mo₂C/C nanosheets tremendously promote the electrochemical activity and operate stability with high specific capacity and extremely stable cycling. In particular, this versatile synthetic strategy can also be extended to other polyoxometalate (such as phosphotungstic acid) to provide greater opportunities for the controlled fabrication of novel hierarchical nanostructures for next‐generation high performance energy storage applications.     

High Performance Lithium‐Ion Batteries Using Layered 2H‐MoTe2 as Anode

The major challenges faced by candidate electrode materials in lithium‐ion batteries (LIBs) include their low electronic and ionic conductivities. 2D van der Waals materials with good electronic conductivity and weak interlayer interaction have been intensively studied in the electrochemical processes involving ion migrations. In particular, molybdenum ditelluride (MoTe₂) has emerged as a new material for energy storage applications. Though 2H‐MoTe₂ with hexagonal semiconducting phase is expected to facilitate more efficient ion insertion/deinsertion than the monoclinic semi‐metallic phase, its application as an anode in LIB has been elusive. Here, 2H‐MoTe₂, prepared by a solid‐state synthesis route, has been employed as an efficient anode with remarkable Li⁺ storage capacity. The as‐prepared 2H‐MoTe₂ electrodes exhibit an initial specific capacity of 432 mAh g^?1 and retain a high reversible specific capacity of 291 mAh g^?1 after 260 cycles at 1.0 A g^?1. Further, a full‐cell prototype is demonstrated by using 2H‐MoTe₂ anode with lithium cobalt oxide cathode, showing a high energy density of 454 Wh kg^?1 (based on the MoTe₂ mass) and capacity retention of 80% over 100 cycles. Synchrotron‐based in situ X‐ray absorption near‐edge structures have revealed the unique lithium reaction pathway and storage mechanism, which is supported by density functional theory based calculations.     

Rationally Designed Silicon Nanostructures as Anode Material for Lithium‐Ion Batteries

Silicon (Si) is promising for high capacity anodes in lithium‐ion batteries due to its high theoretical capacity, low working potential, and natural abundance. However, there are two main drawbacks that impede its further practical applications. One is the huge volume expansion generating during lithiation and delithiation progresses, which leads to severe structural pulverization and subsequently rapid capacity fading of the electrode. The other is the relatively low intrinsic electronic conductivity, therefore, seriously impacting the rate performance. In the past decades, numerous efforts have been devoted for improving the cycling stability and rate capability by rational designs of different nanostructures of Si materials and incorporations with some conductive agents. In this review, the authors summarize the exciting recent research works and focus on not only the synthesis techniques, but also the composition strategies of silicon nanostructures. The advantages and disadvantages of the nanostructures as well as the perspective of this research field are also discussed. We aim to give some reference for engineering application on Si anodes in lithium ion batteries.