Co3O4 Hollow Nanoparticles and Co Organic Complexes Highly Dispersed on N‐Doped Graphene: An Efficient Cathode Catalyst for Li‐O2 Batteries

Rechargeable Li‐O₂ batteries are promising candidates for electric vehicles due to their high energy density. However, the current development of Li‐O₂ batteries demands highly efficient air cathode catalysts for high capacity, good rate capability, and long cycle life. In this work, a hydrothermal‐calcination method is presented to prepare a composite of Co₃O₄ hollow nanoparticles and Co organic complexes highly dispersed on N‐doped graphene (Co–NG), which acts as a bifunctional air cathode catalyst to optimize the electrochemical performances of Li‐O₂ batteries. Co–NG exhibits an outstanding initial discharge capacity up to 19 133 mAh g^?1 at a current density of 200 mA g^?1. In addition, the batteries could sustain 71 cycles at a cutoff capacity of 1000 mAh g^?1 with low overpotentials at the current density of 200 mA g^?1. Co–NG composites are attractive as air cathode catalysts for rechargeable Li‐O₂ 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.     

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.     

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.     

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.     

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.     

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.     

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.     

A Dual Component Catalytic System Composed of Non‐Noble Metal Oxides for Li–O2 Batteries with Enhanced Cyclability

One of the great challenges in the development of lithium–oxygen batteries (Li–O₂ batteries) is to synthesize cost‐effective and efficient electrocatalysts to overcome several issues such as high charge overpotential and poor cycle life. Here, an efficient method is reported to fabricate a dual component electrocatalyst made of MnO₂ nanoparticles supported on 1D Co₃O₄ nanorods (MnO₂–Co₃O₄), and its electrochemical behavior as a non‐noble metal cathode catalyst is demonstrated in Li–O₂ batteries. It is found that the as‐made MnO₂–Co₃O₄ catalyst exhibits an enhanced electrochemical performance, such as increased specific capacity (increase to 4023 mA h g^?1 from 2993 mA h g^?1), low charge overpotential (reduce 350 mV), high rate performance, and superior cyclability up to 150 cycles. The excellent electrochemical performance is attributed to the synergistic effects of the dual component catalytic system.     

Rapid,Microwave‐Assisted,and One‐Pot Synthesis of Magnetic Palladium–CoFe2O4–Graphene Composite Nanosheets and Their Applications as Recyclable Catalysts

Here, a microwave‐assisted approach has been demonstrated to rapidly prepare magnetic Pd–CoFe₂O₄–graphene (GE) composite nanosheets in ethylene glycol (EG) solvent. The generation of both Pd and CoFe₂O₄ nanoparticles is accompanied with the reduction process of graphene oxide (GO) by EG. The surface morphologies and chemical composition of the composite nanosheets are characterized by transmission electron microscopy (TEM), energy‐dispersive X‐ray spectrometer (EDS), powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) measurements. The as‐prepared Pd–CoFe₂O₄–GE composite nanosheets exhibit a remarkable catalytic activity towards the reduction of 4‐nitrophenol by sodium borohydride (NaBH₄) at room temperature. The apparent kinetic rate constant (K _app) of this catalytic reaction could reach about 11.0 × 10^?3 s^?1. Moreover, the CoFe₂O₄ component exhibits a magnetic property, which could make the Pd–CoFe₂O₄–GE composite nanocatalysts separated from the suspension system. The catalytic conversion of the 4‐nitrophenol to 4‐aminophenol could reach 87.2% after four cycles. This work presents a simple, rapid, and versatile method to fabricate both metal and spinel‐type complex oxides on GE nanosheets, providing a new opportunity for their applications in the recyclable catalytic reaction.     

Reduced Graphene Oxide decorated with Manganese Cobalt Oxide as Multifunctional Material for Mechanically Rechargeable and Hybrid Zinc–Air Batteries

Spinel MnCo₂O₄ nanoparticles on nitrogen‐doped reduced graphene oxide (MnCo₂O₄/NGr) are synthesized for advanced zinc–air batteries with remarkable cyclic efficiency and stability. The synthesized MnCo₂O₄/NGr exhibits good oxygen‐reduction reaction (ORR) activity with half‐wave potential E _1/2 of 0.85 V (vs reversible hydrogen electrode (RHE)), comparable to commercial Pt/C with E _1/2 of 0.88 V (vs RHE) along with superior oxygen electrode activity ΔE = 0.91 V for the ORR/OER (oxygen‐evolution reaction) in alkaline media. Durability tests confirm that MnCo₂O₄/NGr is more stable than Pt/C in alkaline environment. MnCo₂O₄/NGr functions with stable discharge profile of 1.2 V at 20 mA cm^?2, large discharge capacity of 707 mAh g^?1_Zn at 40 mA cm^?2 and a high energy density of 813 Wh kg^?1_Zn in a mechanically rechargeable zinc–air battery. The electrically rechargeable MnCo₂O₄/NGr zinc–air battery displays hybrid behavior with both Faradaic and oxygen redox charge–discharge characteristics, operating at higher voltage and providing higher power density and excellent cyclic efficiency of 86% for over 100 cycles compared to Pt/C with efficiency of around 60%. Moreover, hybrid zinc–air battery operates with a stable and energy efficient profile at different current densities.     

Facile Construction of 3D Reduced Graphene Oxide Wrapped Ni3S2 Nanoparticles on Ni Foam for High‐Performance Asymmetric Supercapacitor Electrodes

3D reduced graphene oxide (rGO)‐wrapped Ni₃S₂ nanoparticles on Ni foam with porous structure is successfully synthesized via a facile one‐step solvothermal method. This unique structure and the positive synergistic effect between Ni₃S₂ nanoparticles and graphene can greatly improve the electrochemical performance of the NF@rGO/Ni₃S₂ composite. Detailed electrochemical measurements show that the NF@rGO/Ni₃S₂ composite exhibits excellent supercapacitor performance with a high specific capacitance of 4048 mF cm^?2 (816.8 F g^?1) at a current density of 5 mA cm^?2 (0.98 A g^?1), as well as long cycling ability (93.8% capacitance retention after 6000 cycles at a current density of 25 mA cm^?2). A novel aqueous asymmetric supercapacitor is designed using the NF@rGO/Ni₃S₂ composite as positive electrode and nitrogen‐doped graphene as negative electrode. The assembled device displays an energy density of 32.6 W h kg^?1 at a power density of 399.8 W kg^?1, and maintains 16.7 W h kg^?1 at 8000.2 W kg^?1. This outstanding performance promotes the as‐prepared NF@rGO/Ni₃S₂ composite to be ideal electrode materials for supercapacitors.     

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.     

Flexible Ti‐Doped FeOOH Quantum Dots/Graphene/Bacterial Cellulose Anode for High‐Energy Asymmetric Supercapacitors

Ti‐doped FeOOH quantum dots (QD) decorated on graphene (GN) sheets are designed and fabricated by a facile and scalable synthesis route. Importantly, the Ti‐doped FeOOH QD/GN are successfully dispersed within bacterial cellulose (BC) substrate as bending anode with large loading mass for flexible supercapacitor. By virtue of its favorable architecture, this composite electrode exhibits a remarkable areal capacitance of 3322 mF cm^?2 at 2 mA cm^?2, outstanding cycle performance (94.7% capacitance retention after 6000 cycles), and excellent mechanical strength (68.7 MPa). To push the energy density of flexible supercapacitors, the optimized asymmetric supercapacitor using Mn₃O₄/GN/BC as positive electrode and Ti‐doped FeOOH QD/GN/BC as negative electrode can be cycled reversibly in the operating voltage range of 0–1.8 V and displays ultrahigh areal energy density of 0.541 mWh cm^?2, ultrahigh volumetric energy density of 9.02 mWh cm^?3, reasonable cycling performance (9.4% decay in specific capacitance after 5000 cycles), and good capacitive retention at bending state.     

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.     

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.     

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.     

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.     

Carbon‐Encapsulated Tube‐Wire Co3O4/MnO2 Heterostructure Nanofibers as Anode Material for Sodium‐Ion Batteries

This study presents a general approach for the synthesis of carbon‐encapsulated wire‐in‐tube Co₃O₄/MnO₂ heterostructure nanofibers (Co₃O₄/MnO₂@C) via electrospinning followed by calcination. The as‐synthesized Co₃O₄/MnO₂@C is investigated as the sodium‐ion batteries anode material, which not only exhibits a high reversible capacity of 306 mAh g⁻¹ at 100 mA g⁻¹ over 200 cycles, but also shows a cycling stability of 126 mAh g⁻¹ after 1000 cycles at a high current density of 800 mA g⁻¹. The excellent electrochemical performance can be ascribed to the contribution from carbon‐encapsulated outer‐tube Co₃O₄ and inner‐wire MnO₂ heterostructures, which offer a large internal space and good electrical conductivity. The present work can be helpful in providing new insights into heterostructures for sodium‐ion batteries and other applications.