MoO2@MoS2 Nanoarchitectures for High‐Loading Advanced Lithium‐Ion Battery Anodes

The capacity loading per unit area is of importance as specific capacity while evaluating the lithium‐ion battery anode. However, the low conductivity of several advanced anode materials (such as molybdenum sulfide, MoS₂) prohibits the wide application of materials. Nanostructural engineering becomes a key to overcome the obstacles. A one‐step in situ conversion reaction is employed to synthesize molybdenum oxide (MoO₂)–MoS₂ core–shell nanoarchitectures (MoO₂@MoS₂) by partially sulfiding MoO₂ into MoS₂ using sulfur. The MoO₂@MoS₂ displays a 3D architecture constructed by hundreds of MoS₂ ultrathin sheets with several layers arranged and fixed to an MoO₂ particle vertically with the size in the range of 200–500 nm. MoO₂ acts as the molybdenum source for the synthesis of MoS₂, as well as the conductive substrate. The designed 3D architectures with empty space between MoS₂ layers can prevent the damage originated from volume change of MoS₂ undergoing charge/discharge process. The lithium storage capacities of the MoO₂@MoS₂ 3D architectures are higher and the stability has been significantly improved compared to pure MoS₂. 4 mAh cm^?2 capacity loading of MoO₂@MoS₂ has been achieved with a specific capacity of more than 1000 mAh g^?1.     

Wintersweet Branch‐Like C/C@SnO2/MoS2 Nanofibers as High‐Performance Li and Na‐Ion Battery Anodes

Structure and morphology of molybdenum disulfide (MoS₂) play an important role in improving its reversible lithium storage and sodium storage as anodes. In this study, a facile method is developed to prepare C/C@SnO₂/MoS₂ nanofibers with MoS₂ nanoflakes anchoring on the core–shell C/C@SnO₂ nanofibers through hydrothermal reaction. By adjusting the concentration of MoS₂ precursors, the synthesized MoS₂ with different slabs dimensions, size, and morphologies are obtained, constituting budding and blooming wintersweet branch‐like composite structure, respectively. Owing to scattered MoS₂ nanoparticles and sporadic MoS₂ nanoflakes, the budding wintersweet branch‐like composite nanofibers processes less slabs of staking in number and large specific surface area. Benefiting from the exposed C@SnO₂ shell layer, the synergistic effect among SnO₂, carbon, and MoS₂ is strengthened, which maximizes the advantage of each material to exhibit stable specific capacities of 650 and 230 mAh g^?1 for Li‐ion batteries and Na‐ion batteries after 200 cycles.     

Nanoparticles Engineering for Lithium‐Ion Batteries

Lithium‐ion batteries (LIBs) have been extensively investigated due to the ever‐increasing demand for new electrode materials for electric vehicles (EVs) and clean energy storage. A wide variety of nano/microstructured LIBs electrode materials are hitherto created via self‐assembly, ranging from 0D nanospheres; 1D nanorods, nanowires, or nanobelts; and 2D nanofilms to 3D nanorod array films. Nanoparticles can be utilized to build up integrated architectures. Understanding of nanoparticles’ self‐assembly may provide information about their organization into large aggregates through low‐cost, high‐efficiency, and large‐scale synthesis. Here, the focus is on the recent advances in preparing hierarchically nano/microstructured electrode materials via self‐assembly. The hierarchical electrode materials are assembled from single component, binary to multicomponent building blocks via different driving forces including diverse chemical bonds and non‐covalent interactions. It is expected that nanoparticle engineering by high‐efficient self‐assembly process will impact the development of high‐performance electrode materials and high‐performance LIBs or other rechargeable batteries.     

Hollow Silica Spheres Embedded in a Porous Carbon Matrix and Its Superior Performance as the Anode for Lithium‐Ion Batteries

Silica (SiO₂) is regarded as one of the most promising anode materials for lithium‐ion batteries due to the high theoretical specific capacity and extremely low cost. However, the low intrinsic electrical conductivity and the big volume change during charge/discharge cycles result in a poor electrochemical performance. Here, hollow silica spheres embedded in porous carbon (HSS–C) composites are synthesized and investigated as an anode material for lithium‐ion batteries. The HSS–C composites demonstrate a high specific capacity of about 910 mA h g^?1 at a rate of 200 mA g^?1 after 150 cycles and exhibit good rate capability. The porous carbon with a large surface area and void space filled both inside and outside of the hollow silica spheres acts as an excellent conductive layer to enhance the overall conductivity of the electrode, shortens the diffusion path length for the transport of lithium ions, and also buffers the volume change accompanied with lithium‐ion insertion/extraction processes.     

Copper‐Based Nanomaterials for High‐Performance Lithium‐Ion Batteries

With the increasing energy demands for electronic devices and electrical vehicles, anode materials for lithium‐ion batteries with high specific capacity, good cyclic and rate performance become one of the focal areas of research. A class of them is the copper‐based nanomaterials that have thermal and chemical stability, high theoretical specific capacity, low price and environment friendliness. Now this kind of nanomaterials has been recognized as one of the critical materials for lithium‐ion batteries due to the predicted future market growth. Current status of different copper‐based materials which produced already are discussed. In this review, comprehensive summaries and evaluations are given in synthesis strategies, tailored material properties and different electrochemical performance. Recent progress of general copper‐based nanomaterials for lithium‐ion batteries is carefully presented.     

Electrospinning Synthesis of Porous NiCoO2 Nanofibers as High‐Performance Anode for Lithium‐Ion Batteries

Nanostructured ternary/mixed transition metal oxides have attracted considerable attentions because of their high‐capacity and high‐rate capability in the electrochemical energy storage applications, but facile large‐scale fabrication with desired nanostructures still remains a great challenge. To overcome this, a facile synthesis of porous NiCoO₂ nanofibers composed of interconnected nanoparticles via an electrospinning–annealing strategy is reported herein. When examined as anode materials for lithium‐ion batteries, the as‐prepared porous NiCoO₂ nanofibers demonstrate superior lithium storage properties, delivering a high discharge capacity of 945 mA h g^?1 after 140 cycles at 100 mA g^?1 and a high rate capacity of 523 mA h g^?1 at 2000 mA g^?1. This excellent electrochemical performance could be ascribed to the novel hierarchical nanoparticle‐nanofiber assembly structure, which can not only buffer the volumetric changes upon lithiation/delithiation processes but also provide enlarged surface sites for lithium storage and facilitate the charge/electrolyte diffusion. Notably, a facile synthetic strategy for fabrication of ternary/mixed metal oxides with 1D nanostructures, which is promising for energy‐related applications, is provided.     

Porous Silicon@Polythiophene Core–Shell Nanospheres for Lithium‐Ion Batteries

Polythiophene‐coated porous silicon core–shell nanospheres (Si@PTh) composite are synthesized by a simple chemical oxidative polymerization approach. The polythiophene acts as a flexible layer to hold silicon grains when they are repeatedly alloying/dealloying with lithium during the discharge/charge process. The long lifespan and high‐current‐density rate ­capability (at a current of 8 A g^?1) of the Si@PTh composite are vastly improved compared with as‐prepared Si spheres. Typically, these Si@PTh composite electrodes achieve a reversible capacity of 1130.5 mA h g^?1 at 1 A g^?1 current density after 500 cycles, and can even possess a discharge capacity up to 451.8 mA h g^?1 at 8 A g^?1. The improved electrochemical performance can be ascribed to the synergy effects of the flexible PTh coating and the distinctive core–shell nanospheres with porous structure, which can largely alleviate the volume expansion of the Si during alloying with lithium.     

High Rate and Long Cycle Life of a CNT/rGO/Si Nanoparticle Composite Anode for Lithium‐Ion Batteries

Si nanoparticle (Si‐NP) composite anode with high rate and long cycle life is an attractive anode material for lithium‐ion battery (LIB) in hybrid electric vehicle (HEV)/pure electric vehicle (PEV). In this work, a carbon nanotube (CNT)/reduced graphene oxide (rGO)/Si nanoparticle composite with alternated structure as Li‐ion battery anode is prepared. In this structure, rGO completely wraps the entire Si/CNT networks by different layers and CNT networks provide fast electron transport pathways with reduced solid‐state diffusion, so that the stable solid‐electrolyte interphase layer can form on the whole surface of the matrix instead of on single Si nanoparticle, which ensure the high cycle stability to achieve the excellent cycle performance. As a result, the CNT/rGO/Si‐NP anode exhibits high performances with long cycle life (≈455 mAh g^?1 at 15 A g^?1 after 2000 cycles), high specific charge capacity (≈2250 mAh g^?1 at 0.2 A g^?1, ≈650 mAh g^?1 at 15 A g^?1), and fast charge/discharge rates (up to 16 A g^?1). This nanostructure anode with facile and low‐cost synthesis method, as well as excellent electrochemical performances, makes it attractive for the long life cycles at high rate of the next generation LIB applications in HEV/PEV.     

Synthesis of Porous NiO Nanorods as High‐Performance Anode Materials for Lithium‐Ion Batteries

1D nanostructured metal oxides with porous structure have drawn wide attention to being used as high‐performance anode materials for lithium‐ion batteries (LIBs). This study puts forward a simple and scalable strategy to synthesize porous NiO nanorods with the help of a thermal treatment of metal‐organic frameworks in air. The NiO nanorods with an average diameter of approximately 38 nm are composed of nanosized primary particles. When evaluated as anode materials for LIBs, an initial discharge capacity of 743 mA h g^?1 is obtained at a current density of 100 mA g^?1, and a high reversible capacity is still maintained as high as 700 mA h g^?1 even after 60 charge–discharge cycles. The excellent electrochemical performance is mainly ascribed to the 1D porous structure.     

MFe2O4 and MFe@Oxide Core–Shell Nanoparticles Anchored on N‐Doped Graphene Sheets for Synergistically Enhancing Lithium Storage Performance and Electrocatalytic Activity for Oxygen Reduction Reactions

The intrinsically low electric conductivity and self‐aggregation of MFe₂O₄ during charge/discharge affect their lithium storage performance and electrocatalytic activity. To mitigate these problems, it is shown that N‐doped graphene sheets (NGS), as a highly conductive platform, finely disperse the MFe₂O₄ nanoparticles and rapidly shuttle electrons to and from the MFe₂O₄ nanoparticles. Moreover, by forming a metal@oxide core–shell nanostructure, fast electron transfer from the exterior oxide layer to NGS is achieved. Introducing NGS into MFe₂O₄ allows the composites to exhibit the comparable specific capacity (based on the total mass) to MFe₂O₄, although over 10 wt% of NGS contributes a low specific capacity of around 320–400 mAh g^?1. More importantly, introducing NGS significantly increases the cycling stability performance: 97.5% (CoFe₂O₄/NGS) and ≈100% (NiFe₂O₄/NGS) of the specific capacities have been retained after 80 cycles, far higher than the capacity retentions of CoFe₂O₄ (35.3%) and NiFe₂O₄ (43.7%) tested under otherwise identical conditions. Also demonstrated are the excellent rate capabilities of the composites. For catalyzing the oxygen reduction reaction, the activity is significantly improved when the MFe₂O₄ nanoparticles are transformed into metal@oxide core–shell nanostructure, mainly because the core–shell nanostructure exhibits lower charge transfer resistance.     

Controllable Formation of Niobium Nitride/Nitrogen‐Doped Graphene Nanocomposites as Anode Materials for Lithium‐Ion Capacitors

Niobium nitride/nitrogen‐doped graphene nanosheet hybrid materials are prepared by a simple hydrothermal method combined with ammonia annealing and their electrochemical performance is reported. It is found by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) that the as‐obtained niobium nitride nanoparticles are about 10–15 nm in size and homogeneously anchored on graphene. A non‐aqueous lithium‐ion capacitor is fabricated with an optimized mass loading of activated carbon cathode and the niobium nitride/nitrogen‐doped graphene nanosheet anode, which delivers high energy densities of 122.7–98.4 W h kg^?1 at power densities of 100–2000 W kg^?1, respectively. The capacity retention is 81.7% after 1000 cycles at a current density of 500 mA g^?1. The high energy and power of this hybrid capacitor bridges the gap between conventional high specific energy lithium‐ion batteries and high specific power electrochemical capacitors, which holds great potential applications in energy storage for hybrid electric vehicles.     

Three‐Dimensional Multilayer Assemblies of MoS2/Reduced Graphene Oxide for High‐Performance Lithium Ion Batteries

Three‐dimensional (3D) multilayer molybdenum disulfide (MoS₂)/reduced graphene oxide (RGO) nanocomposites are prepared by a solution‐processed self‐assembly based on the interaction using different sizes of MoS₂ and GO nanosheets followed by in situ chemical reduction. 3D multilayer assemblies with MoS₂ wrapped by large RGO nanosheets and good interface are observed by transmission electron microscopy. The interaction of Na⁺ ions with oxygen‐containing groups of GO is also investigated. The measurement of lithium ion batteries (LIBs) shows that MoS₂/RGO anode nanocomposite with a weight ratio of MoS₂ to GO of 3:1 exhibits an excellent rate performance of 750 mAh g^?1 at 3 A g^?1 outperforming many previous studies and a high reversible capacity up to ≈1180 mAh g^?1 after 80 cycles at 100 mA g^?1. Good rate performance and high capacity of MoS₂/RGO with 3D unique layered‐structures are attributed to the combined effects of continuous conductive networks of RGO, good interface facilitating charge transfer, and strong RGO sheets preventing the volume expansion. Results indicate that 3D multilayer MoS₂/RGO prepared by a facile solution‐processed assembly can be developed to be an excellent nanoarchitecture for high‐performance LIBs.     

Towards Excellent Anodes for Li‐Ion Batteries with High Capacity and Super Long Lifespan: Confining Ultrasmall Sn Particles into N‐Rich Graphene‐Based Nanosheets

Sn is regarded as a promising anode material for Li‐ion batteries due to high capacity and cost effectiveness. Hitherto large‐scale fabrication of Sn‐based materials while achieving both high capacity and long cycle life remains challenging, but it is highly required for its realization in practical applications. Furthermore, low melting point always casts shadow over the morphology‐controllable preparation, and leads to multistep or high‐cost processes. Here, a facile and scalable method is devised for a 2D hybrid structure of Sn@graphene‐based nanosheets incorporating of optimized nitrogen species (≈13 wt%). Distinct from conventional Sn–C composites, the fairly N‐rich carbon nanosheets liberate limited potential of low N doping, induce massive extra Li‐storage sites, and encourage a high capacity significantly. In addition, these abundantly anchored heteroatoms also promote the homogeneous dispersion and robust confinement of ultrasmall Sn nanoparticles into the flexible graphene‐based nanosheets. This elastic encapsulation towards Sn nanoparticles admirably maintains structural integrity through effective remission of volume expansion, demonstrating a super long‐term cyclic stability for 1000 cycles. This structural and componential engineering offers a significant implication for rational design of materials in extended areas of energy conversion and storage.     

High‐Pressure Evaporation‐Based Nanoporous Black Sn for Enhanced Performance of Lithium‐Ion Battery Anodes

Increasing the surface area to improve chemical activity is an unending task from conventional catalysis to recently emerging electrochemical energy conversion and storage. Here, a simple, vacuum‐deposition‐based method to form nanoporous structures of metals is reported. By utilizing thermal evaporation at a high pressure, fractal‐like nanoporous structures of Sn with porosity exceeding 98% are synthesized. The obtained nanostructure consists of nanoparticle aggregates, and the morphology can be controlled by adjusting the working pressure. The formation of the nanoporous structure is explained by homogeneous nucleation and diffusion‐limited aggregation, where nanoparticles produced by the repeated collisions of evaporated atoms adhere to the substrate without diffusion, forming porous aggregates. Due to the easy oxidation of Sn, the constituent nanoparticles are covered with amorphous SnO_x and crystalline SnO phases. When the nanoporous Sn/SnO_x aggregates are applied to a lithium‐ion battery anode through direct deposition on a Cu foil current collector without binders or conducting additives, the nanoporous Sn/SnO_x anode shows greatly enhanced cyclability and exceptional rate performance compared to those of a dense Sn thin film anode. The approach investigated in this work is expected to provide a new platform to other fields that require highly porous structures.     

Vanadium Pentoxide‐Based Cathode Materials for Lithium‐Ion Batteries: Morphology Control,Carbon Hybridization,and Cation Doping

Vanadium pentoxide (V₂O₅) is a promising cathode material for high‐performance lithium‐ion batteries (LIBs) because of its high specific capacity, low cost, and abundant source. However, the practical application of V₂O₅ in commercial LIBs is still hindered by its intrinsic low ionic diffusion coefficient and moderate electrical conductivity. In the past decades, progressive accomplishments have been achieved that rely on the synthesis of nanostructured materials, carbon hybridization, and cation doping. Generally, fabrication of nanostructured electrode materials can effectively decrease the ion and electron transport distances while carbon hybridization and cation doping are able to significantly increase the electrical conductivity and diffusion coefficient of Li⁺. Implementation of these strategies addresses the problems that are related to the ionic and electronic conductivity of V₂O₅. Accordingly, the electrochemical performances of V₂O₅‐based cathodes are significantly improved in terms of discharge capacity, cycling stability, and rate capability. In this review, the recent advances in the synthesis of V₂O₅‐based cathode materials are highlighted that focus on the fabrication of nanostructured materials, carbon hybridization, and cation doping.     

Full Protection for Graphene‐Incorporated Micro‐/Nanocomposites Containing Ultra‐small Active Nanoparticles: the Best Li‐Storage Properties

In recent years, graphene‐incorporated micro‐/nanocomposites represent one of the hottest developing directions for the composite materials. However, a large number of active nanoparticles (NPs) are still in the unprotected state in most constructed graphene‐containing designs, which will seriously impair the effects of the graphene additives. Here, a fully protected Fe₃O₄‐based micro‐/nanocomposite (G/Fe₃O₄@C) is rationally developed by carbon‐boxing the common graphene/Fe₃O₄ microparticulates (G/Fe₃O₄). The processes and results of full protection are tracked in detail and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, and nitrogen absorption–desorption isotherms, as well as scanning and transition electron microscopy. When used as the anode for lithium‐ion batteries, the fully protected G/Fe₃O₄@C exhibits the best lithium‐storage properties in terms of the highest rate capabilities and the longest cycle life compared to the common G/Fe₃O₄ composites and commercial Fe₃O₄ products. These much improved properties are mainly attributed to its novel structural features including complete protection of active Fe₃O₄ nanoparticles by the surface carbon box, a robust conductive network composed of nitrogen‐doped graphene nanosheets, ultra‐small Fe₃O₄ NPs of 4–5 nm, abundant mesopores to accommodate the volume variation during cycling, and micrometer‐sized secondary particles.