Epitaxial Growth of Urchin‐Like CoSe2 Nanorods from Electrospun Co‐Embedded Porous Carbon Nanofibers and Their Superior Lithium Storage Properties

A facile synthesis of porous graphitic carbon nanofibers (CNFs) with encapsulated Co nanoparticles (denote as Co@CNFs) via electrospinning and subsequent annealing is reported. The in situ generated Co nanoparticles (NPs) promote the CNF graphitization under a low temperature of 700 °C, which simultaneously results in the porous structure of the Co@CNFs with a large surface area (416 m² g^?1). Furthermore, urchin‐like CoSe₂ nanorods are epitaxially grown from the Co@CNFs via a facile hydrothermal selenation, in which the embedded Co NPs serve as directing seeds and sacrificial Co‐source, and CoSe₂ nanorods are rooted into the CNFs (denote as CoSe₂@CNFs). When used as anode materials for lithium ion batteries, the CoSe₂@CNFs demonstrate superior lithium storage properties, delivering a high reversible capacity of 1405 mA h g^?1 after 300 cycles at a current density of 200 mA g^?1. The enhanced lithium storage performance can be attributed to the novel hybrid structure, namely, the porous and graphitic CNFs can not only facilitate the charge/ion transfer but also buffer the volume changes of the electrode during lithiation/delithiation processes. More importantly, a general strategy is provided to graphitize amorphous carbon materials via the use of in situ generated transition metal nanoparticles as catalyst.     

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.     

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.     

Facile Fabrication of Bicomponent CoO/CoFe2O4‐N‐Doped Graphene Hybrids with Ultrahigh Lithium Storage Capacity

A facile strategy is developed to fabricate bicomponent CoO/CoFe₂O₄‐N‐doped graphene hybrids (CoO/CoFe₂O₄‐NG). These hybrids are demonstrated to be potential high‐performance anodes for lithium‐ion batteries (LIBs). The CoO/CoFe₂O₄ nanoplatelets are finely dispersed on the surface of N‐doped graphene nanosheets (CoO/CoFe₂O₄‐NG). The CoO/CoFe₂O₄‐NG electrode exhibits ultrahigh specific capacity with 1172 mA h g^?1 at 500 mA g^?1 and 970 mA h g^?1 at 1000 mA g^?1 as well as excellent cycle stability due to the synergetic effects of N‐doped graphene and CoO/CoFe₂O₄ nanoplatelets. The well‐dispersed bicomponent CoO/CoFe₂O₄ is responsible for the high specific capacity. The N‐doped graphene with high specific surface area has dual roles: to provide active sites for dispersing the CoO/CoFe₂O₄ species and to function as an electrical conducting matrix for fast charge transfer. This method provides a simple and efficient way to configure the hybridized electrode materials with high lithium storage capacity.     

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.     

Sulfur Immobilized in Hierarchically Porous Structured Carbon as Cathodes for Lithium–Sulfur Battery with Improved Electrochemical Performance

In order to overcome the main obstacles for lithium–sulfur batteries, such as poor conductivity of sulfur, polysulfide intermediate dissolution, and large volume change generated during the cycle process, a hard‐template route is developed to synthesize large‐surface area carbon with abundant micropores and mesopores to immobilize sulfur species. The microstructures of the C/S hybrids are investigated using field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, Raman spectroscopy, X‐ray photoelectron spectroscopy, nitrogen adsorption–desorption isotherms, and electrochemical impedance spectroscopy techniques. The large surface and porous structure can effectively alleviate large strain due to the lithiation/delithiation process. More importantly, the micropores can effectively confine small molecules of sulfur in the form of S_2–4, avoiding loss of active S species and dissolution of high‐order lithium polysulfides. The porous C/S hybrids show significantly enhanced electrochemical performance with good cycling stability, high specific capacity, and rate capability. The C/S‐39 hybrid with an optimal content of 39 wt% S shows a reversible capacity of 780 mA h g^?1 after 100 cycles at the current density of 100 mA g^?1. Even at a current density of 5 A g^?1, the reversible capacity of C/S‐39 can still maintain at 420 mA h g^?1 after 60 cycles. This strategy offers a new way for solving long‐term reversibility obstacle and designing new cathode electrode architectures.     

Metal Oxide Nanomaterials with Nitrogen‐Doped Graphene‐Silk Nanofiber Complexes as Templates

Fabricating electrode materials with superior electrochemical performance remains a challenge. Here, a simple but effective strategy for the formation of metal oxide nanomaterials with superior performance has been developed. Silk protein nanofibers adhered on reduced graphene oxide (rGO) sheets are used as templates to regulate the formation of nanostructured iron oxide composites, achieving porous nanorod structures that could not be attained in control experiments. These porous nanorods demonstrate superior electrochemical performance as electrodes with retention of a capacity of 1495 mAh g^?1 after 180 cycles at 0.2 C and a rate capability of 900 mAh g^?1 at 2 C discharge rate. These new rGO/silk composite templates provide a more controllable environment for Fe₂O₃ fabrication, resulting in improved nanostructures and superior electrical performance. The strategy developed here should also be more broadly applicable in the design of metal oxide nanomaterials with specialized structures and useful performance.     

Encapsulating Tin Dioxide@Porous Carbon in Carbon Tubes: A Fiber‐in‐Tube Hierarchical Nanostructure for Superior Capacity and Long‐Life Lithium Storage

A novel fiber‐in‐tube hierarchical nanostructure of SnO₂@porous carbon in carbon tubes (SnO₂@PC/CTs) is creatively designed and synthesized though a carbon coating on scalable electrospun hybrid nanofibers template and a post‐etching technique. This 1D nanoarchitecture consists of double carbon‐buffering matrixes, i.e., the external carbon tubular shell and the internal porous carbon skeleton, which can work synergistically to address the various issues of SnO₂ nanoanode operation, such as pulverization, particle aggregation, and vulnerable electrical contacts between the SnO₂ nanoparticles and the carbon conductors. Thus, the as‐obtained SnO₂@PC/CTs nanohybrids used as a lithium‐ion‐battery anode exhibits a higher reversible capacity of 1045 mA h g^?1 at 0.5 A g^?1 after 300 cycles as well as a high‐rate cycling stability after 1000 cycles. The enhanced performance can be attributed to the wonderful merits of the external carbon protective shell for preserving the integrity of the overall electrode, and the internal porous carbon skeleton for inhibiting the aggregation and electrical isolation of the active particles during cycling.     

Porous NiO hollow quasi-nanospheres derived from a new metal-organic framework template as high-performance anode materials for lithium ion batteries

Porous hollow metal oxides derived from nanoscaled metal-organic framework (MOF) have drawn tremendous attention due to their high electrochemical performance in advanced Li-ion batteries (LIBs). In this work, porous NiO hollow quasi-nanospheres were fabricated by an ordinary refluxing reaction combination of a thermal decomposition of new nanostructured Ni-MOF, i.e., {Ni₃(HCOO)₆·DMF}_n. When evaluated as an anode material for lithium ion batteries, the MOF derived NiO electrode exhibits high capacity, good cycling stability and rate performance (760 mAh g^?1 at 200 mA g^?1 after 100 cycles, 392 mAh g^?1 at 3200 mA g^?1). This superior lithium storage performance is mainly attributed to the unique hollow and porous nanostructure of the as-synthesized NiO, which offer enough space to accommodate the dramstic volume change and alleviate the pulverization problem during the repeated lithiation/delithiation processes, and provide more electro-active sites for fast electrochemical reactions as well as promote lithium ions and electrons transfer at the electrolyte/electrode interface.     

Formation of Sn@C Yolk–Shell Nanospheres and Core–Sheath Nanowires for Highly Reversible Lithium Storage

As one promising anode material with high theoretical capacity, metallic tin has attracted much research interest in the field of lithium‐ion batteries. Here, two types of tin/carbon (Sn@C) core–shell nanostructures with inner buffering voids are fabricated from SnO₂ hollow nanospheres via a facile chemical vapor deposition (CVD) method. The crystallinity and surface topography of SnO₂ hollow nanospheres are found to affect the morphology of resultant Sn@C materials. Sn@C yolk–shell nanospheres and core–sheath nanowires are obtained from the as‐prepared SnO₂ and high‐temperature annealed SnO₂ nanospheres, respectively. The unique Sn@C nanostructures can mitigate the agglomeration/pulverization of Sn nanoparticles and electrical disconnection from the current collector caused by the large volume change during the lithium alloying/dealloying process. Both Sn@C yolk–shell and core–sheath nanostructures show stable cycling performance up to 500 cycles with specific capacities of ca. 430 and 520 mA h g^?1, respectively.     

Graphene‐Based Phosphorus‐Doped Carbon as Anode Material for High‐Performance Sodium‐Ion Batteries

Graphene‐based phosphorus‐doped carbon (GPC) is prepared through a facile and scalable thermal annealing method by triphenylphosphine and graphite oxide as precursor. The P atoms are successfully doped into few layer graphene with two forms of P–O and P–C bands. The GPC used as anode material for Na‐ion batteries delivers a high charge capacity 284.8 mAh g^?1 at a current density of 50 mA g^?1 after 60 cycles. Superior cycling performance is also shown at high charge?discharge rate: a stable charge capacity 145.6 mAh g^?1 can be achieved at the current density of 500 mA g^?1 after 600 cycles. The result demonstrates that the GPC electrode exhibits good electrochemical performance (higher reversible charge capacity, super rate capability, and long‐term cycling stability). The excellent electrochemical performance originated from the large interlayer distance, large amount of defects, vacancies, and active site caused by P atoms doping. The relationship of P atoms doping amount with the Na storage properties is also discussed. This superior sodium storage performance of GPC makes it as a promising alternative anode material for sodium‐ion batteries.     

Facile Synthesis of Porous MnO Microspheres for High‐Performance Lithium‐Ion Batteries

Manganese oxide is a highly promising anode material of lithium‐ion batteries (LIBs) for its low insertion voltage and high reversible capacity. Porous MnO microspheres are prepared by a facile method in this work. As an anode material of LIB, it can deliver a high reversible capacity up to 1234.2 mA h g^?1 after 300 cycles at 0.2 C, and a capacity of 690.0 mA h g^?1 in the 500th cycle at 2 C. The capacity increase with cycling can be attributed to the growth of reversible polymer/gel‐like film, and the better cycling stability and the superior rate performance can be attributed to the featured structure of the microspheres composed of nanoparticles with a short transport path for lithium ions, a large specific surface, and material/electrolyte contact area. The results suggest that the porous MnO microspheres can function as a promising anode material for high‐performance LIBs.     

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.     

Tailoring MoS2 Ultrathin Sheets Anchored on Graphene Flexible Supports for Superstable Lithium‐Ion Battery Anodes

2D MoS₂ has a significant capacity decay due to the stack of layers during the charge/discharge process, which has seriously restricted its practical application in lithium‐ion batteries. Herein, a simple preform‐in situ process to fabricate vertically grown MoS₂ nanosheets with 8–12 layers anchored on reduced graphene oxide (rGO) flexible supports is presented. As an anode in MoS₂/rGO//Li half‐cell, the MoS₂/rGO electrode shows a high initial coulomb efficiency (84.1%) and excellent capacity retention (84.7% after 100 cycles) at a current density of 100 mA g^?1. Moreover, the MoS₂/rGO electrode keeps capacity as high as 786 mAh g^?1 after 1000 cycles with minimum degradation of 54 µAh g^?1 cycle^?1 after being further tested at a high current density of 1000 mA g^?1. When evaluated in a MoS₂/rGO//LiCoO₂ full‐cell, it delivers an initial charge capacity of 153 mAh g^?1 at a current density of 100 mA g^?1 and achieves an energy density of 208 Wh kg^?1 under the power density of 220 W kg^?1.     

A Facile Method for Synthesis of Porous NiCo2O4 Nanorods as a High‐Performance Anode Material for Li‐Ion Batteries

Porous electrode materials with large specific surface area, relatively short diffusion path, and higher electrical conductivity, which display both better rate capabilities and good cycle lives, have huge benefits for practical applications in lithium‐ion batteries. Here, uniform porous NiCo₂O₄ nanorods (PNNs) with pore‐size distribution in the range of 10–30 nm and lengths of up to several micrometers are synthesized through a convenient oxalate co‐precipitation method followed by a calcining process. The PNN electrode exhibits high reversible capacity and outstanding cycling stability (after 150 cycles still maintain about 650 mA h g^?1 at a current density of 100 mA g^?1), as well as high Coulombic efficiency (>98%). Moreover, the PNNs also exhibit an excellent rate performance, and deliver a stable reversible specific capacity of 450 mA h g^?1 even at 2000 mA g^?1. These results demonstrate that the PNNs are promising anode materials for high‐performance Li‐ion batteries.     

Highly Dispersed ZnSe Nanoparticles Embedded in N‐Doped Porous Carbon Matrix as an Anode for Potassium Ion Batteries

Advanced nanostructured functional materials obtained from the precursors of metal–organic frameworks show several unique advantages, including plentiful porous structures and large specific surface areas. Based on this, designed and constructed are highly dispersed ZnSe nanoparticles anchored in a N‐doped porous carbon rhombic dodecahedron (ZnSe@NDPC) by a sequential high‐temperature pyrolysis and selenization method. The specific synthesis process involves a two‐step heat treatment of the template‐engaged reaction between zinc‐based zeolitic imidazolate framework (ZIF‐8) and selenium power. By optimizing the calcination temperature, the as‐synthesized ZnSe@NDPC‐700 as an advanced anode of potassium ion batteries demonstrates the best electrochemical performance, including a high capacity (262.8 mA h g^?1 over 200 cycles at 100 mA g^?1) and a good rate capability (109.4 mA h g^?1 at 2000 mA g^?1 and 52.8 mA h g^?1 at 5000 mA g^?1). Moreover, the capacitance and diffusion mechanisms are also investigated by the qualitative and quantitate analysis, finally accounting for the superior K storage.     

Liquid‐Crystal‐Mediated Self‐Assembly of Porous α‐Fe2O3 Nanorods on PEDOT:PSS‐Functionalized Graphene as a Flexible Ternary Architecture for Capacitive Energy Storage

A novel aqueous‐based self‐assembly approach to a composite of iron oxide nanorods on conductive‐polymer (CP)‐functionalized, ultralarge graphene oxide (GO) liquid crystals (LCs) is demonstrated here for the fabrication of a flexible hybrid material for charge capacitive application. Uniform decoration of α‐Fe₂O₃ nanorods on a poly(3,4‐ethylene‐dioxythiophene): poly(styrenesulfonate) (PEDOT:PSS)‐functionalized, ultralarge GO scaffold results in a 3D interconnected layer‐by‐layer (LBL) architecture. This advanced interpenetrating network of ternary components is lightweight, foldable, and possesses highly conductive pathways for facile ion transportation and charge storage, making it promising for high‐performance energy‐storage applications. Having such structural merits and good synergistic effects, the flexible architecture exhibits a high specific discharge capacitance of 875 F g^?1 and excellent volumetric specific capacitance of 868 F cm^?3 at 5 mV s^?1, as well as a promising energy density of 118 W h kg^?1 (at 0.5 A g^?1) and promising cyclability, with capacity retention of 100% after 5000 charge–discharge (CD) cycles. This synthesis method provides a simple, yet efficient approach for the solution‐processed LBL insertion of the hematite nanorods (HNR) into CP‐functionalized novel composite structure. It provides great promise for the fabrication of a variety of metal‐oxide (MO)‐nanomaterial‐based binder and current collector‐free flexible composite electrodes for high‐performance energy‐storage applications.     

Encapsulation of SnO2/Sn Nanoparticles into Mesoporous Carbon Nanowires and its Excellent Lithium Storage Properties

A peculiar nanostructure of encapsulation of SnO₂/Sn nanoparticles into mesoporous carbon nanowires (CNWs) has been successfully fabricated by a facile strategy and confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high‐resolution TEM (HRTEM), X‐ray diffraction (XRD), BET, energy‐dispersive X‐ray (EDX) spectrometer, and X‐ray photoelectron spectroscopy (XPS) characterizations. The 1D mesoporous CNWs effectively accommodate the strain of volume change, prevent the aggregation and pulverization of nanostructured SnO₂/Sn, and facilitate electron and ion transport throughout the electrode. Moreover, the void space surrounding SnO₂/Sn nanoparticles also provides buffer spaces for the volumetric change of SnO₂/Sn during cycling, thus resulting in excellent cycling performance as potential anode materials for lithium‐ion batteries. Even after 499 cycles, a reversible capacity of 949.4 mAh g^?1 is retained at 800 mA g^?1. Its unique architecture should be responsible for the superior electrochemical performance.     

Ge Nanoparticles Encapsulated in Interconnected Hollow Carbon Boxes as Anodes for Sodium Ion and Lithium Ion Batteries with Enhanced Electrochemical Performance

A carbothermal reaction route to Ge nanoparticle homogeneously encapsulated hollow carbon boxes from NH₄H₃Ge₂O₆/resorcinol formaldehyde precursors is designed, using NH₄H₃Ge₂O₆ as a Ge precursor from commercial GeO₂ and NH₄OH. The Ge/C hybrid anode for sodium ion battery displays a higher Na⁺ storage capacity of 346 mA h g^?1 after 500 cycles at a current density of 100 mA h g^?1, almost approaching the theoretical capacity of Ge. Furthermore, Ge/C anode shows significantly improved electrochemical performance for Li⁺ storage, showing a higher initial Coulombic efficiency of 85.1% and a superior reversible capacity of 1336 mA h g^?1 at a high current density of 200 mA g^?1 after 150 cycles. An excellent rate capability with a capacity of 825 mA h g^?1 at a current density of 4.0 A g^?1 can be obtained based on Ge/C anodes. The enhanced electrochemical performance can be attributed to the unique microstructures of Ge/C hybrid anode. The internal void space of hollow carbon boxes can accommodate the volume expansion of Ge during lithiation or sodiation process, thus preserving the structural integrity of electrode material. The interconnected carbon shell can increase the electronic conductivity of the electrode, resulting in the high rate capability and cycling stability.