Template‐Free Fabrication of Hollow NiO–Carbon Hybrid Nanoparticle Aggregates with Improved Lithium Storage

Hollow NiO–carbon hybrid nanoparticle aggregates are fabricated through an environmental template‐free solvothermal alcoholysis route. Controlled hollow structure is achieved by adjusting the ratio of ethylene glycol to water and reaction time of solvothermal alcoholysis. Amorphous carbon can be loaded on the NiO nanoparticles uniformly in the solvothermal alcoholysis process, and the subsequent calcination results in the formation of hollow NiO–C hybrid nanoparticle aggregates. As anode materials for lithium‐ion batteries, it exhibits a stable reversible capacity of 622 mAh g^?1, and capacity retention keeps over 90.7% after 100 cycles at constant current density of 200 mA g^?1. The NiO–C electrode also exhibits good rate capabilities. The unique hollow structures can shorten the length of Li‐ion diffusion and offer a sufficient void space, which sufficiently alleviates the mechanical stress caused by volume change. The hybrid carbon in the particles renders the electrode having a good electronic conductivity. Here, the hollow NiO‐C hybrid electrode exhibits excellent electrochemical performance.     

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.     

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.     

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.     

Synthesis of hollow silica-sulfur composite nanospheres towards stable lithium-sulfur battery

Herein, porous hollow silica nanospheres were prepared via a facile sol-gel process in an inverse microemulsion, using self-assemblies of chiral amphiphile as a soft template and fine water droplets as a hard template. The shells of the hollow silica nanospheres are composed of flake-like nanoparticles with dense big holes on the surface. After covering a layer of sulfur on the silica nanospheres, followed by hydrothermal treatment in a D-glucose aqueous solution, silica-sulfur and silica-sulfur-carbon nanospheres were successfully fabricated. The silica-sulfur composites exhibit a stable capacity of 454 mAh g^?1 at current density of 335 mA g^?1 after 100 cycles with capacity retention of 85%, demonstrating a promising cathode material for rechargeable lithium-sulfur batteries. We believe that the approach for synthesis of porous hollow silica nanospheres and its carbon spheroidal shell can also be applicable for designing other electrode materials for energy storage.     

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.     

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.     

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.     

Red phosphorus encapsulated in porous carbon derived from cigarette filter solid waste as a promising anode material for lithium-ion batteries

Red phosphorus (RP) is considered to be one of the promising anode materials for lithium-ion batteries (LIBs) on account of its high theoretical capacity (2596 mAh g^?1), abundant resources, and environmental friendliness. However, the intrinsic insulating nature and large volume change during lithium insertion/extraction process lead to drastic capacity loss upon cycling. Recently, great attention has been devoted to constructing P-based composites via mixing with carbon materials. Here, a novel P/C composite, in which red P nanoparticles were homogeneously distributed in cigarette filter-derived porous carbon (CPC), was fabricated by vaporization-condensation method. Due to the unique characteristics of porous carbon, including high specific area, good conductivity, and rich internal porous structure, CPC obtained by means of heat treatment that serves as conductive matrix to load red P could be of great benefits, which can not only improve the overall electrical conductivity but also mitigate the volume expansion issues. As a result, the RP/CPC composite as an anode material for LIBs delivers a good cycling stability (500 mAh g^?1 at 100 mA g^?1 with a high Coulombic efficiency above 99% after 50 cycles) and rate capability (355 mAh g^?1 even at 1000 mA g^?1).     

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.     

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.     

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.     

Insert Zn Nanoparticles into the 3D Porous Carbon Ultrathin Films as a Superior Anode Material for Lithium Ion Battery

A flexible strategy is exploited to insert Zn nanoparticles into the pores of highly stable 3D network of carbon ultrathin films (P‐Zn/C) that can effectively localize the postformed Zn nanoparticles, thereby solving the problem of structural degradation, and thus achieve improved anode performance. A maximum capacity of 657.3 mA h g⁻¹ at a current density of 200 mA g⁻¹ after 50 cycles is achieved for P‐Zn/C. Even at a high current density of 2 A g⁻¹, a capacity of 653 mA h g⁻¹ is maintained after 1000 cycles, indicating that it could be a promising anode for lithium ion batteries. By comparing the capacitive and diffusion contribution qualitatively and quantitatively, the result reveals that the enhanced electrochemical performance mainly originates from the pseudocapacitance storage mechanism.     

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.     

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 and Scalable Synthesis of Si@void@C Embedded in Interconnected 3D Porous Carbon Architecture for High Performance Lithium-Ion Batteries

Si-based materials possess huge potential as an excellent anode material for Li-ion batteries. However, how to realize scalable synthesis of Si-based anode with a long cycling life and high-performance is still a critical challenge. Here a water-in-oil microemulsion process followed by UV illumination, calcination, and hydrothermal method to produce yolk-shell Si@void@C embedded in interconnected 3D porous carbon network architecture using silicon nanoparticles is reported. As a result, the sample Si@void@C/C-2 electrode has achieved a reversible capacity of 1160 mA h g⁻¹ at 0.2 A g⁻¹ after 300 cycles and a stable long cycling life of 480 mA h g⁻¹ at 1 A g⁻¹ after 1000 cycles. A full battery with the synthesized anode shows a capacity of 128 mA h g⁻¹ at 0.2 A g⁻¹ as well as good cycling stability after 1100th cycles. Such excellent electrochemical performance is ascribed to its unique structure, the yolk-shell void space, highly robust carbon shells and interconnected porous carbon nets that can improve the conductivity of the electrode, buffer the volume expansion, and also suppress Si nanoparticles stress variation. This water-in oil system makes it possible for mass production of environmentally friendly synthesis of core–shell structure.     

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.     

Nitrogen-doped carbon nanofiber decorated LiFePO<Subscript>4</Subscript> composites with superior performance for lithium-ion batteries

Nitrogen-doped carbon nanofiber (NCNF) decorated LiFePO₄ (LFP) composites are synthesized via an in situ hydrothermal growth method. Electrochemical performance results show that the embedded NCNF can improve electron and ion transfer, thereby resulting in excellent cycling performance. The as-prepared LFP and NCNF composites exhibit excellent electrochemical properties with discharge capacities of 188.9 mAh g^?1 (at 0.2 C) maintained at 167.9 mAh g^?1 even after 200 charge/discharge cycles. The electrode also presents a good rate capability of 10 C and a reversible specific capacity as high as 95.7 mAh g^?1. LFP composites are a potential alternative high-performing anode material for lithium ion batteries.     

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.