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.     

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.     

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.     

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.     

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.     

Hierarchically Porous NaCoPO4–Co3O4 Hollow Microspheres for Flexible Asymmetric Solid‐State Supercapacitors

A template‐free hydrothermal method is developed to prepare hierarchical hollow precursors. An inside‐out Ostwald ripening mechanism is proposed to explain the formation of the hollow structure. After the calcination in the air, hierarchically meso/macroporous NaCoPO₄–Co₃O₄ hollow microspheres can easily be obtained. When being evaluated as electrode materials for a supercapacitor, the hierarchically porous NaCoPO₄–Co₃O₄ hollow microspheres electrode shows a specific capacitance of 268 F g^?1 at 0.8 A g^?1 and offers a good cycle life. More importantly, the obtained materials are successfully applied to fabricate flexible solid‐state asymmetric supercapacitors. The device exhibits a specific capacitance of 28.6 mF cm^?2 at 0.1 mA cm^?2, a good cycling stability with only 5.5% loss of capacitance after 5000 cycles, and good mechanical flexibility under different bending angles, which confirms that the hierarchically porous NaCoPO₄–Co₃O₄ hollow microspheres are promising active materials for the flexible supercapacitor.     

Enhanced lithium storage performance of a self-assembled hierarchical porous Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/VGCF hybrid high-capacity anode material for lithium-ion batteries

A Co₃O₄/vapor-grown carbon fiber (VGCF) hybrid material is prepared by a facile approach, namely, via liquid-phase carbonate precipitation followed by thermal decomposition of the precipitate at 380 °C for 2 h in argon gas flow. The material is characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller specific surface area analysis, and carbon elemental analysis. The Co₃O₄ in the hybrid material exhibits the morphology of porous submicron secondary particles which are self assembled from enormous cubic-phase crystalline Co₃O₄ nanograins. The electrochemical performance of the hybrid as a high-capacity conversion-type anode material for lithium-ion batteries is investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic discharge/charge methods. The hybrid material demonstrates high specific capacity, good rate capability, and good long-term cyclability, which are far superior to those of the pristine Co₃O₄ material prepared under similar conditions. For example, the reversible charge capacities of the hybrid can reach 1100–1150 mAh g^?1 at a lower current density of 0.1 or 0.2 A g^?1 and remain 600 mAh g^?1 at the high current density of 5 A g^?1. After 300 cycles at 0.5 A g^?1, a high charge capacity of 850 mAh g^?1 is retained. The enhanced electrochemical performance is attributed to the incorporated VGCFs as well as the porous structure and the smaller nanograins of the Co₃O₄ active material.     

3D Array of Bi2S3 Nanorods Supported on Ni Foam as a Highly Efficient Integrated Oxygen Electrode for the Lithium‐Oxygen Battery

Bismuth sulfide nanorod array is directly grown on nickel foam (R‐Bi₂S₃/NF) to serve as a completely carbon and binder‐free 3D porous oxygen electrode material for lithium‐oxygen (Li‐O₂) batteries. The synergistic effect of the fast kinetics of electron transport and gas and electrolyte diffusion provided by the continuous free‐standing network structure and the excellent electrocatalytic activity of the bismuth sulfide nanorod array enables outstanding performance of the oxygen electrode. Li‐O₂ battery with the free‐standing R‐Bi₂S₃/NF oxygen electrode exhibits high energy efficiency (78.7%), good rate capability (4464 mA h g⁻¹ at 1500 mA g⁻¹), as well as excellent cyclability (146 cycles) while maintaining a moderate specific capacity of 1000 mA h g⁻¹. The effect of cathodes with different reactant (O₂) and intermediate (LiO₂) adsorbability on the product (Li₂O₂) growth model is studied by first‐principle calculations. The strong O₂ adsorption and weak LiO₂ adsorption on Bi₂S₃ drives the growth of large‐size Li₂O₂ particles via solution growth model. Remarkably, the large‐area pouch‐type Li‐O₂ battery delivers an energy density of 330 Wh kg⁻¹. The present results open up a promising avenue toward developing novel electrode architecture for high‐performance Li‐O₂ batteries through controlling morphology and functionality of porous electrodes.     

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.     

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.     

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.     

Dandelion-like mesoporous Co<Subscript>3</Subscript>O<Subscript>4</Subscript> as anode materials for lithium ion batteries

A dandelion-like mesoporous Co₃O₄ was fabricated and employed as anode materials of lithium ion batteries (LIBs). The architecture and electrochemical performance of dandelion-like mesoporous Co₃O₄ were investigated through structure characterization and galvanostatic charge/discharge test. The as-prepared dandelion-like mesoporous Co₃O₄ consisted of well-distributed nanoneedles (about 40 nm in width and about 5 μm in length) with rich micropores. Electrochemical experiments illustrated that the as-prepared dandelion-like mesoporous Co₃O₄ as anode materials of LIBs exhibited high reversible specific capacity of 1430.0 mA h g^?1 and 1013.4 mA h g^?1 at the current density of 0.2 A g^?1 for the first and 100th cycle, respectively. The outstanding lithium storage properties of the as-prepared dandelion-like mesoporous Co₃O₄ might be attributed to its dandelion-like mesoporous nanostructure together with an open space between adjacent nanoneedle networks promoting the intercalation/deintercalation of lithium ions and the charge transfer on the electrode. The enhanced capacity as well as its high-rate capability made the as-prepared dandelion-like mesoporous Co₃O₄ to be a good candidate as a high-performance anode material for LIBs.     

General Synthesis and Lithium Storage Properties of Metal Oxides/MnO2 Hierarchical Hollow Hybrid Spheres

Metal oxides/MnO₂ hierarchical hollow hybrid nanostructures have attracted significant attention because of their wide potential applications. However, the exploration of a general synthetic approach for fabricating hierarchical hollow hybrid nanostructures is still a great challenge. Herein, a “penetration‐carbonization and reduction‐coating–annealing” route is presented for the generalized synthesis of metal oxides/MnO₂ hierarchical hollow hybrid spheres, including NiO/MnO₂, Co₃O₄/MnO₂, and CuO/MnO₂. Because of the unique hierarchical hollow hybrid nanostructures, NiO/MnO₂ nanomaterials possess a desirable capacity (1520 mA h g⁻¹) and outstanding cyclic stability (909 mA h g⁻¹ at the 200th cycle) as Li‐ion battery anode materials. The work reported herein can not only pave the way for the generalized synthetic strategy of metal oxides/MnO₂ hierarchical hollow hybrid nanostructures, but also provide a promising application of NiO/MnO₂ nanomaterials for Li‐ion battery anode.     

Enhancement of electrochemical properties of Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> as anode materials for lithium-ion batteries by transition metal doping

Misfit-layered calcium cobaltites (Ca₃Co₄O₉, Ca₃Co_3.9Fe_0.1O₉, and Ca₃Co_3.9Mn_0.1O₉), as anode materials for lithium-ion batteries, were synthesized by a simple hydro-decomposition method. All synthesized samples do not show any impurity phase. They exhibited plate-like particle with the particle size of 1–2 μm. The specific capacities of doped samples showed higher electrochemical performance compared to the undoped sample. After charge/discharge of 50 cycles, the specific capacities of Ca₃Co₄O₉, Ca₃Co_3.9Fe_0.1O₉, and Ca₃Co_3.9Mn_0.1O₉ were 343, 562, and 581 mAh g^?1, respectively. The doped samples showed an increase of over 60% compared to the undoped sample. The cyclic voltammetry profile of the doped samples showed the enhanced reactivity corresponding to their improved electrochemical performance. The capacity improvement of doped samples resulted from the metal oxide/Li conversion reactions, volume change, and high reactivity.     

A High‐Performance Anode Material for Li‐Ion Batteries Based on a Vertically Aligned CNTs/NiCo2O4 Core/Shell Structure

3D vertically aligned carbon nanotubes (CNTs)/NiCo₂O₄ core/shell structures are successfully synthesized as binder‐free anode materials for Li‐ion batteries (LIBs) via a facile electrochemical deposition method followed by subsequent annealing in air. The vertically aligned CNTs/NiCo₂O₄ core/shell structures are used as binder‐free anode materials for LIBs and exhibit high and stable reversible capacity (1147.6 mAhg^?1 at 100 mAg^?1), excellent rate capability (712.9 mAh g^?1 at 1000 mAg^?1), and good cycle stability (no capacity fading over 200 cycles). The improved performance of these LIBs is attributed to the unique 3D vertically aligned CNTs/NiCo₂O₄ core/shell structures, which support high electron conductivity, fast ion/electron transport in the electrode and at the electrolyte/electrode interface, and accommodate the volume change during cycling. Furthermore, the synthetic strategy presented can be easily extended to fabricate other metal oxides with a controlled core/shell structure, which may be a promising electrode material for high‐performance LIBs.     

Hierarchical Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@C hollow microspheres with high capacity as an anode material for lithium-ion batteries

Three-dimensional hierarchical Co₃O₄@C hollow microspheres (Co₃O₄@C HSs) are successfully fabricated by a facile and scalable method. The Co₃O₄@C HSs are composed of numerous Co₃O₄ nanoparticles uniformly coated by a thin layer of carbon. Due to its stable 3D hierarchical hollow structure and uniform carbon coating, the Co₃O₄@C HSs exhibit excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs). The Co₃O₄@C HSs electrode delivers a high reversible specific capacity, excellent cycling stability (1672 mAh g^?1 after 100 cycles at 0.2 A g^?1 and 842.7 mAh g^?1 after 600 cycles at 1 A g^?1), and prominent rate performance (580.9 mAh g^?1 at 5 A g^?1). The excellent electrochemical performance makes this 3D hierarchical Co₃O₄@C HS a potential candidate for the anode materials of the next-generation LIBs. In addition, this simple synthetic strategy should also be applicable for synthesizing other 3D hierarchical metal oxide/C composites for energy storage and conversion.     

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.     

Study of spin–phonon coupling in LiFe1 − xMnxPO4olivines

LiFe_{1 − x}Mn_xPO₄ olivines are promising material for improved performance of Li‐ion batteries. Spin–phonon coupling of LiFe_{1 − x}Mn_xPO₄ (x = 0, 0.3, 0.5) olivines is studied through temperature‐dependent Raman spectroscopy. Among the observed phonon modes, the external mode at ~263 cm⁻¹ is directly correlated with the motions of magnetic Fe²⁺/Mn²⁺ ions. This mode displays anomalous temperature‐dependent behavior near the Néel temperature, indicating a coupling of this mode with spin ordering. As Mn doping increases, the anomalous behavior becomes clearly weaker, indicating the spin–phonon coupling quickly decreases. Our analyses show that the quick decrease of spin–phonon coupling is due to decrease of the strength of spin–phonon coupling, but not change of spin‐ordering feature with Mn doping. Importantly, we suggest that the low electrochemical activity of LiMnPO₄ is correlated with the weak spin–phonon coupling strength, but not with the weak ferromagnetic ground state. Our work would play an important role as a guide in improving the performances of future Li‐ion batteries. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

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.