Germanium Nanograin Decoration on Carbon Shell: Boosting Lithium‐Storage Properties of Silicon Nanoparticles

A novel heterostructured Si@C@Ge anode is developed via a two‐step sol–gel method. A facile and straightforward Ge decoration significantly boosts the Li‐storage performance of core–shell Si@C nanoparticles on both mechanics and kinetics. The Si@C@Ge anode shows unprecedented electrochemical performance in terms of accessible capacity, cycling stability, and rate capability when compared to those of a core–shell Si@C anode. Based on the experimental results and analysis of the mechanism, it is evident that high‐conductivity Ge nanograins on the surface facilitates the Li diffusivity and electron transport and guarantees high ion accessibility. Moreover, it is the Ge nanograins that serve as buffering cushion to tolerate the mechanic strain distribution on the electrode during lithiation/delithiation processes.     

GeO2 Encapsulated Ge Nanostructure with Enhanced Lithium‐Storage Properties

Germanium (Ge)‐based nanostructures, especially those with germanium dioxide (GeO₂), have drawn great interest for applications in lithium (Li)‐ion batteries due to their ultrahigh theoretical Li⁺ storage capability (8.4 Li/Ge). However, GeO₂ in conventional Ge(s)/GeO₂(c) (where (c) means the core and (s) means the shell) composite anodes with Ge shell outside GeO₂ undergoes an irreversible conversion reaction, which restricts the maximum capacity of such batteries to 1126 mAhg^?1 (the equivalent of storing 4.4 Li⁺). In this work, a porous GeO₂(s)/Ge(c) nanostructure with GeO₂ shell outside Ge cores are successfully fabricated utilizing the Kirkendall effect and used as a lithium‐ion battery anode, giving a substantially improved capacity of 1333.5 mAhg^?1 at a current density of 0.1 Ag^?1 after 30 cycles and a stable long‐time cycle performance after 100 cycles at a current density of 0.5 A g^?1. The enhanced battery performance is attributed to the improved reversibility of GeO₂ lithiation/delithiation processes catalyzed by Ge in the properly structured porous GeO₂(s)/Ge(c) nanostructure.     

Porous Si Nanowires from Cheap Metallurgical Silicon Stabilized by a Surface Oxide Layer for Lithium Ion Batteries

In the quest to develop next generation lithium ion battery anode materials, satisfactory electrochemical performance and low material/fabrication cost are the most desirable features. In this article, porous Si nanowires are synthesized by a cost‐effective metal‐assisted chemical etching method using cheap metallurgical silicon as feedstock. More importantly, a thin oxide layer (≈3 nm) formed on the surface of porous Si nanowires stabilizes the cycling performance of lithium ion batteries. Such an oxide coating is able to constrain the huge volume expansion of the underlying Si, yet it is thin enough to ensure good permeability for both lithium ions and electrons. Therefore, the extraordinary storage capacity of Si can be well retained in prolonged electrochemical cycles. Specifically, Si/SiO_x nanowires deliver a reversible capacity of 1503 mAh g^?1 at the 560th cycle at a current density of 600 mA g^?1, demonstrating an average of only 0.04% drop per cycle compared with its initial capacity. Furthermore, the highly porous structure and thin Si wall facilitate the electrolyte penetration and shorten the solid‐state lithium transportation path, respectively. As a result, stable and satisfactory reversible capacities of 1297, 976, 761, 548, and 282 mAh g^?1 are delivered at current densities of 1200, 2400, 3600, 4800, and 7200 mA g^?1, respectively.     

Highly Connected Silicon–Copper Alloy Mixture Nanotubes as High‐Rate and Durable Anode Materials for Lithium‐Ion Batteries

Seeking high‐capacity, high‐rate, and durable anode materials for lithium‐ion batteries (LIBs) has been a crucial aspect to promote the use of electric vehicles and other portable electronics. Here, a novel alloy‐forming approach to convert amorphous Si (a‐Si)‐coated copper oxide (CuO) core–shell nanowires (NWs) into hollow and highly interconnected Si–Cu alloy (mixture) nanotubes is reported. Upon a simple H₂ annealing, the CuO cores are reduced and diffused out to alloy with the a‐Si shell, producing highly interconnected hollow Si–Cu alloy nanotubes, which can serve as high‐capacity and self‐conductive anode structures with robust mechanical support. A high specific capacity of 1010 mAh g^?1 (or 780 mAh g^?1) has been achieved after 1000 cycles at 3.4 A g^?1 (or 20 A g^?1), with a capacity retention rate of ≈84% (≈88%), without the use of any binder or conductive agent. Remarkably, they can survive an extremely fast charging rate at 70 A g^?1 for 35 runs (corresponding to one full cycle in 30 s) and recover 88% capacity. This novel alloy‐nanotube structure could represent an ideal candidate to fulfill the true potential of Si‐loaded LIB applications.     

“Brain‐Coral‐Like” Mesoporous Hollow CoS2@N‐Doped Graphitic Carbon Nanoshells as Efficient Sulfur Reservoirs for Lithium–Sulfur Batteries

Hollow carbon materials are considered promising sulfur reservoirs for lithium–sulfur batteries owing to their internal void space and porous conductive shell, providing high loading and utilization of sulfur. Since the pores in carbon materials play a critical role in the infusion of sulfur, access of the electrolyte, and the passage of lithium polysulfides (LPSs), the creation and tuning of hierarchical pore structures is strongly required to improve the electrochemical properties of sulfur/porous carbon composites, but remains a major challenge. Herein, a “brain‐coral‐like” mesoporous hollow carbon nanostructure consisting of an in situ‐grown N‐doped graphitic carbon nanoshell (NGCNs) matrix and embedded CoS₂ nanoparticles as an efficient sulfur host is presented. The rational synthetic design based on metal–organic framework chemistry furnishes unusual multiple porosity in a carbon scaffold with a macrohollow in the core and microhollows and mesopores in the shell, without the use of any surfactant or template. The CoS₂@NGCNs/S composite electrode facilitates high sulfur loading (75 wt%), strong adsorption of LPSs, efficient reaction kinetics, and stable cycle performance (903 mAh g^?1 at 0.1 C after 100 cycles), derived from the synergetic effects of the dual hollow features, chemically active CoS₂, and the conductive and mesoporous N‐doped carbon matrix.     

Carbon‐Interconnected Ge Nanocrystals as an Anode with Ultra‐Long‐Term Cyclability for Lithium Ion Batteries

Germanium (Ge) possesses a great potential as a high‐capacity anode material for lithium ion batteries but suffers from its poor capacity retention and rate capability due to significant volume expansion by lithiation. Here, a facile synthetic route is introduced for producing nanometer‐sized Ge crystallites interconnected by carbon (GEC) via thermal decomposition of a Ge‐citrate complex followed by a calcination process in an inert atmosphere. The GEC electrode shows outstanding electrochemical performance, i.e., an almost 98.8% capacity retention of 1232 mAh g^?1, even after 1000 cycles at the rate of C/2. Importantly, a high discharge capacity of 880 mAh g^?1 is maintained at the very high rate of 10 C. The excellent anode performance of GEC stems from both effective buffering of carbon anchored to the Ge nanocrystals and the high open porosity of the GEC aggregated powder with an average pore diameter of 32 nm. Furthermore, the interfacial layer formed between Ge and carbon plays an essential role in prolonging the cycle life. The GEC electrode can be successfully employed as an anode for next generation lithium ion batteries.     

Ultra‐High Capacity Lithium‐Ion Batteries with Hierarchical CoO Nanowire Clusters as Binder Free Electrodes

Although transition metal oxide electrodes have large lithium storage capacity, they often suffer from low rate capability, poor cycling stability, and unclear additional capacity. In this paper, CoO nanowire clusters (NWCs) composed of ultra‐small nanoparticles (≈10 nm) directly grown on copper current collector are fabricated and evaluated as an anode of binder‐free lithium‐ion batteries, which exhibits an ultra‐high capacity and good rate capability. At a rate of 1 C (716 mA g^?1), a reversible capacity as high as 1516.2 mA h g^?1 is obtained, and even when the current density is increased to 5 C, a capacity of 1330.5 mA h g^?1 could still be maintained. Importantly, the origins of the additional capacity are investigated in detail, with the results suggesting that pseudocapacitive charge and the higher‐oxidation‐state products are jointly responsible for the large additional capacity. In addition, nanoreactors for the CoO nanowires are fabricated by coating the CoO nanowires with amorphous silica shells. This hierarchical core–shell CoO@SiO₂ NWC electrode achieves an improved cycling stability without degrading the high capacity and good rate capability compared to the uncoated CoO NWCs electrode.     

Graphene‐Based Mesoporous SnO2 with Enhanced Electrochemical Performance for Lithium‐Ion Batteries

Graphene‐based metal oxides generally show outstanding electrochemical performance due to the superior properties of graphene. However, the aggregation of active metal oxide nanoparticles on the graphene surface may result in a capacity fading and poor cycle performance. Here, a mesostructured graphene‐based SnO₂ composite is prepared through in situ growth of SnO₂ particles on the graphene surface using cetyltrimethylammonium bromide as the structure‐directing agent. This novel mesoporous composite inherits the advantages of graphene nanosheets and mesoporous materials and exhibits higher reversible capacity, better cycle performance, and better rate capability compared to pure mesoporous SnO₂ and graphene‐based nonporous SnO₂. It is concluded that the synergetic effect between graphene and mesostructure benefits the improvement of the electrochemical properties of the hybrid composites. This facile method may offer an attractive alternative approach for preparation of the graphene‐based mesoporous composites as high‐ performance electrodes for lithium‐ion batteries.     

Nanostructured Silicon Anodes for High‐Performance Lithium‐Ion Batteries

Despite the high theoretical capacity of Si anodes, the electrochemical performance of Si anodes is hampered by severe volume changes during lithiation and delithiation, leading to poor cyclability and eventual electrode failure. Nanostructured silicon and its nanocomposite electrodes could overcome this problem holding back the deployment of Si anodes in lithium‐ion batteries (LIBs) by providing facile strain relaxation, short lithium diffusion distances, enhanced mass transport, and effective electrical contact. Here, the recent progress in nanostructured Si‐based anode materials such as nanoparticles, nanotubes, nanowires, porous Si, and their respective composite materials and fabrication processes in the application of LIBs have been reviewed. The ability of nanostructured Si materials in addressing the above mentioned challenges have been highlighted. Future research directions in the field of nanostructured Si anode materials for LIBs are summarized.     

Novel Type‐II InAs/AlSb Core–Shell Nanowires and Their Enhanced Negative Photocurrent for Efficient Photodetection

The control of optical and transport properties of semiconductor heterostructures is crucial for engineering new nanoscale photonic and electrical devices with diverse functions. Core–shell nanowires are evident examples of how tailoring the structure, i.e., the shell layer, plays a key role in the device performance. However, III–V semiconductors bandgap tuning has not yet been fully explored in nanowires. Here, a novel InAs/AlSb core–shell nanowire heterostructure is reported grown by molecular beam epitaxy and its application for room temperature infrared photodetection. The core–shell nanowires are dislocation‐free with small chemical intermixing at the interfaces. They also exhibit remarkable radiative emission efficiency, which is attributed to efficient surface passivation and quantum confinement induced by the shell. A high‐performance core–shell nanowire phototransistor is also demonstrated with negative photoresponse. In comparison with simple InAs nanowire phototransistor, the core–shell nanowire phototransistor has a dark current two orders of magnitude smaller and a sixfold improvement in photocurrent signal‐to‐noise ratio. The main factors for the improved photodetector performance are the surface passivation, the oxide in the AlSb shell and the type‐II bandgap alignment. The study demonstrates the potential of type‐II core–shell nanowires for the next generation of photodetectors on silicon.     

Engineered Interfusion of Hollow Nitrogen‐Doped Carbon Nanospheres for Improving Electrochemical Behavior and Energy Density of Lithium–Sulfur Batteries

Hollow nanostructures are one of promising sulfur host materials for lithium–sulfur (Li–S) batteries, but the ineffective contact among discrete particles usually generates overall poor electrical conductivity and low volumetric energy density. A new interfused hollow nitrogen‐doped carbon (HNPC) material, derived from imidazolium‐based ionic polymer (ImIP)‐encapsulated zeolitic imidazolate framework‐8 (ZIF‐8), is reported. A novel method for ZIF‐8 disassembly induced by the decomposition of the ImIP shell is proposed. The unique structural superiority gives the resultant electrodes remarkable cycling stability, high rate capability, and large volumetric energy density. A stable reversible discharge capacity over 562 mA h g^?1 at 2 C is achieved after prolonged cycling for 800 cycles and the average capacity decay per cycle is as low as 0.035%. The electrochemical performance achieved greatly surpasses that of ZIF‐8‐derived carbon matrices and conventional nitrogen‐doped carbon materials. This proposed methodology opens a new avenue for the design of hollow‐structured carbon nanoarchitectures with target functionalities.     

Regulated Breathing Effect of Silicon Negative Electrode for Dramatically Enhanced Performance of Li‐Ion Battery

Si is an attractive negative electrode material for lithium ion batteries due to its high specific capacity (≈3600 mAh g^–1). However, the huge volume swelling and shrinking during cycling, which mimics a breathing effect at the material/electrode/cell level, leads to several coupled issues including fracture of Si particles, unstable solid electrolyte interphase, and low Coulombic efficiency. In this work, the regulation of the breathing effect is reported by using Si–C yolk–shell nanocomposite which has been well‐developed by other researchers. The focus is on understanding how the nanoscaled materials design impacts the mechanical and electrochemical response at electrode level. For the first time, it is possible to observe one order of magnitude of reduction on breathing effect at the electrode level during cycling: the electrode thickness variation reduced down to 10%, comparing with 100% in the electrode with Si nanoparticles as active materials. The Si–C yolk–shell nanocomposite electrode exhibits excellent capacity retention and high cycle efficiency. In situ transmission electron microscopy and finite element simulations consistently reveals that the dramatically enhanced performance is associated with the regulated breathing of the Si in the new composite, therefore the suppression of the overall electrode expansion.     

Core–Shell Ge@Graphene@TiO2 Nanofibers as a High‐Capacity and Cycle‐Stable Anode for Lithium and Sodium Ion Battery

Germanium is considered as a promising anode material because of its comparable lithium and sodium storage capability, but it usually exhibits poor cycling stability due to the large volume variation during lithium or sodium uptake and release processes. In this paper, germanium@graphene nanofibers are first obtained through electrospinning followed by calcination. Then atomic layer deposition is used to fabricate germanium@graphene@TiO₂ core–shell nanofibers (Ge@G@TiO₂ NFs) as anode materials for lithium and sodium ion batteries (LIBs and SIBs). Graphene and TiO₂ can double protect the germanium nanofibers in charge and discharge processes. The Ge@G@TiO₂ NFs composite as an anode material is versatile and exhibits enhanced electrochemical performance for LIBs and SIBs. The capacity of the Ge@G@TiO₂ NFs composite can be maintained at 1050 mA h g^?1 (100th cycle) and 182 mA h g^?1 (250th cycle) for LIBs and SIBs, respectively, at a current density of 100 mA g^?1, showing high capacity and good cycling stability (much better than that of Ge nanofibers or Ge@G nanofibers).     

Silicon‐Based Self‐Assemblies for High Volumetric Capacity Li‐Ion Batteries via Effective Stress Management

Silicon nanoparticles (Si NPs) have been considered as promising anode materials for next‐generation lithium‐ion batteries, but the practical issues such as mechanical structure instability and low volumetric energy density limit their development. At present, the functional energy‐storing architectures based on Si NPs building blocks have been proposed to solve the adverse effects of nanostructures, but designing ideal functional architectures with excellent electrochemical performance is still a significant challenge. This study shows that the effective stress evolution management is applied for self‐assembled functional architectures via cross‐scale simulation and the simulated stress evolution can be a guide to design a scalable self‐assembled hierarchical Si@TiO₂@C (SA‐SiTC) based on core–shell Si@TiO₂ nanoscale building blocks. It is found that the carbon filler and TiO₂ layer can effectively reduce the risk of cracking during (de)lithiation, ensuring the stability of the mechanical structure of SA‐SiTC. The SA‐SiTC electrode shows long cycling stability (842.6 mAh g^?1 after 1000 cycles at 2 A g^?1), high volumetric capacity (174 mAh cm^?3), high initial Coulombic efficiency (80.9%), and stable solid‐electrolyte interphase (SEI) layer. This work provides insight into the development of the structural stable Si‐based anodes with long cycle life and high volumetric energy density for practical energy applications.     

Yolk–Shell Structured Assembly of Bamboo‐Like Nitrogen‐Doped Carbon Nanotubes Embedded with Co Nanocrystals and Their Application as Cathode Material for Li–S Batteries

Despite their high theoretical specific capacity (1675 mA h g^?1), the practical application of Li–S batteries remains limited because the capacity rapidly degrades through severe dissolution of lithium polysulfide and the rate capability is low because of the low electronic conductivity of sulfur. This paper describes novel hierarchical yolk–shell microspheres comprising 1D bamboo‐like N‐doped carbon nanotubes (CNTs) encapsulating Co nanoparticles (Co@BNCNTs YS microspheres) as efficient cathode hosts for Li–S batteries. The microspheres are produced via a two‐step process that involves generation of the microsphere followed by N‐doped CNTs growth. The hierarchical yolk–shell structure enables efficient sulfur loading and mitigates the dissolution of lithium polysulfides, and metallic Co and N doping improves the chemical affinity of the microspheres with sulfur species. Accordingly, a Co@BNCNTs YS microsphere‐based cathode containing 64 wt% sulfur exhibits a high discharge capacity of 700.2 mA h g^?1 after 400 cycles at a current density of 1 C (based on the mass of sulfur); this corresponds to a good capacity retention of 76% and capacity fading rate of 0.06% per cycle with an excellent rate performance (752 mA h g^?1 at 2.0 C) when applied as cathode hosts for Li–S batteries.     

Multicore–Shell Bi@N‐doped Carbon Nanospheres for High Power Density and Long Cycle Life Sodium‐ and Potassium‐Ion Anodes

Bismuth (Bi) is an attractive material as anodes for both sodium‐ion batteries (NIBs) and potassium‐ion batteries (KIBs), because it has a high theoretical gravimetric capacity (386 mAh g^?1) and high volumetric capacity (3800 mAh L^?1). The main challenges associated with Bi anodes are structural degradation and instability of the solid electrolyte interphase (SEI) resulting from the huge volume change during charge/discharge. Here, a multicore–shell structured Bi@N‐doped carbon (Bi@N‐C) anode is designed that addresses these issues. The nanosized Bi spheres are encapsulated by a conductive porous N‐doped carbon shell that not only prevents the volume expansion during charge/discharge but also constructs a stable SEI during cycling. The Bi@N‐C exhibits unprecedented rate capability and long cycle life for both NIBs (235 mAh g^?1 after 2000 cycles at 10 A g^?1) and KIBs (152 mAh g^?1 at 100 A g^?1). The kinetic analysis reveals the outstanding electrochemical performance can be attributed to significant pseudocapacitance behavior upon cycling.     

Honeycomb‐Like Spherical Cathode Host Constructed from Hollow Metallic and Polar Co9S8 Tubules for Advanced Lithium–Sulfur Batteries

The practical application of lithium‐sulfur (Li‐S) batteries remains remote because of rapid capacity fade caused by the low conductivity of sulfur, dissolution of intermediate lithium polysulfides, severe volumetric expansion, and slow redox kinetics of polysulfide intermediates. Here, to address these obstacles, a new sulfiphilic and highly conductive honeycomb‐like spherical cathode host constructed from hollow metallic and polar Co₉S₈ tubes is designed. Co₉S₈ can effectively bind polar polysulfides for prolonged cycle life, due to the strong chemisorptive capability for immobilizing the polysulfide species. The hollow structure, as the sulfur host, can further prevent polysulfide dissolution and offer sufficient space to accommodate the necessary volume expansion. Well‐aligned tubular arrays provide a conduit for rapid conduction of electrons and Li‐ions. More importantly, the experimental results and theoretical calculations show that Co₉S₈ plays an important catalytic role in improving the electrochemical reaction kinetics. When used as cathode materials for Li–S batteries, the S@Co₉S₈ composite cathode exhibits high capacity and an exceptional stable cycling life demonstrated by tests of 600 cycles at 1 C with a very low capacity decay rate of only ≈0.026% per cycle.     

Crystallinity‐Controlled Germanium Nanowire Arrays: Potential Field Emitters

We report a simple method, oblique angle deposition, to directly synthesize aligned Ge nanowire arrays on a Si substrate. This process is accomplished by tilting the Si substrate and adjusting the incident angle of the evaporated Ge vapor flux with respect to the substrate normal to 87°. The resultant crystallinity of the Ge nanostructures can be tuned to either amorphous or poly‐ and single‐crystalline, depending on the substrate temperature and evaporation rate. The effects of thermal treatment on the morphology and structure of the Ge nanowires are discussed in detail. The field‐emission measurements show that increasing the annealing temperatures to about 550 °C results in a gradual increase in the maximum current density and a decrease in the turn‐on voltage, because of the decreased wire density originating from melting of the Ge nanowires. The field‐enhancement factor analysis shows there is an optimum range for Ge wire density and aspect ratio to obtain good emission performance. Ge nanowire arrays might find potential application in the field emitters of the future.     

Sn‐Based Nanoparticles Encapsulated in a Porous 3D Graphene Network: Advanced Anodes for High‐Rate and Long Life Li‐Ion Batteries

Sn‐based materials have triggered significant research efforts as anodes for lithium‐storage because of their high theoretical capacity. However, the practical applications of Sn‐based materials are hindered by low capacity release and poor cycle life, which are mainly caused by structural pulverization and large volume changes on cycling. Herein, a surfactant‐assisted assembly method is developed to fabricate 3D nanoarchitectures in which Sn‐based nanoparticles are encapsulated by a porous graphene network. More precisely, the graphene forms a 3D cellular network, the interstices of which only partially filled by the electroactive masses, thus establishing a high concentration of interconnected nanosized pores. While the graphene‐network itself guarantees fast electron transfer, it is the characteristic presence of nanosized pores in our network that leads to the favorable rate capability and cycling stability by i) accommodating the large volume expansion of Sn‐based nanoparticles to ensure integrity of the 3D framework upon cycling and ii) enabling rapid access of Li‐ions into Sn‐based nanoparticles, which are in addition prevented from agglomerating. As a result, the 3D Sn‐based nanoarchitectures deliver excellent electrochemical properties including high rate capability and stable cycle performance. Importantly, this strategy provides a new pathway for the rational engineering of anode materials with large volume changes to achieve improved electrochemical performances.     

Fast and Reversible Li Ion Insertion in Carbon‐Encapsulated Li3VO4 as Anode for Lithium‐Ion Battery

Carbon‐encapsulated Li₃VO₄ is synthesized by a facile environmentally benign solid‐state method with organic metallic precursor VO(C₅H₇O₂)₂ being chosen as both V and carbon sources yielding a core–shell nanostructure with lithium introduced in the subsequent annealing process. The Li₃VO₄ encapsulated with carbon presents exceeding rate capability (a reversible capability of 450, 340, 169, and 106 mAh g^?1 at 0.1 C, 10 C, 50 C, and 80 C, respectively) and long cyclic performance (80% capacity retention after 2000 cycles at 10 C) as an anode in lithium‐ion batteries. The superior performance is derived from the structural features of the carbon‐encapsulated Li₃VO₄ composite with oxygen vacancies in Li₃VO₄, which increase surface energy and could possibly serve as a nucleation center, thus facilitating phase transitions. The in situ generated carbon shell not only facilitates electron transport, but also suppresses Li₃VO₄ particle growth during the calcination process. The encouraging results demonstrate the significant potential of carbon encapsulated Li₃VO₄ for high power batteries. In addition, the simple generic synthesis method is applicable to the fabrication of a variety of electrode materials for batteries and supercapacitors with unique core–shell structure with mesoporous carbon shell.