Sandwich structured graphene-wrapped FeS-graphene nanoribbons with improved cycling stability for lithium ion batteries

Sandwich structured graphene-wrapped FeS-graphene nanoribbons (G@FeS-GNRs) were developed. In this composite, FeS nanoparticles were sandwiched between graphene and graphene nanoribbons. When used as anodes in lithium ion batteries (LIBs), the G@FeS-GNR composite demonstrated an outstanding electrochemical performance. This composite showed high reversible capacity, good rate performance, and enhanced cycling stability owing to the synergy between the electrically conductive graphene, graphene nanoribbons, and FeS. The design concept developed here opens up a new avenue for constructing anodes with improved electrochemical stability for LIBs.

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A composite material of uniformly dispersed sulfur on reduced graphene oxide: Aqueous one-pot synthesis, characterization and excellent performance as the cathode in rechargeable lithium-sulfur batteries

Sulfur-reduced graphene oxide composite (SGC) materials with uniformly dispersed sulfur on reduced graphene oxide sheets have been prepared by a simple aqueous one-pot synthesis method, in which the formation of the composite is achieved through the simultaneous oxidation of sulfide and reduction of graphene oxide. The synthesis process has been tracked ex situ by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectroscopy, which both confirm that the majority of graphene oxide has been reduced during the synthesis reaction. The sulfur contents in the SGC, determined by thermogravimetry and elementary analysis, have been adjusted in the range from 20.9 to 72.5 wt.%. Scanning electron microscope (SEM) and transmission electron microscope (TEM) images reveal that most of the sulfur is uniformly dispersed on the reduced graphene oxide sheets, for which no sulfur in particulate form could be observed. The SGC materials have been tested as the cathode of rechargeable lithium-sulfur (Li-S) batteries, and demonstrated a high reversible capacity and good cycleability. The SGC-63.6%S can deliver a reversible capacity as high as 804 mA·h/g after 80 cycles of charge/discharge at a current density of 312 mA/g (ca. 0.186 C), and 440 mA·h/g after 500 cycles at 1250 mA/g (ca. 0.75 C).      

Hierarchical 3D mesoporous silicon@graphene nanoarchitectures for lithium ion batteries with superior performance

Silicon has been recognized as the most promising anode material for high capacity lithium ion batteries. However, large volume variations during charge and discharge result in pulverization of Si electrodes and fast capacity loss on cycling. This drawback of Si electrodes can be overcome by combination with well-organized graphene foam. In this work, hierarchical three-dimensional carbon-coated mesoporous Si nanospheres@graphene foam （C@Si@GF） nanoarchitectures were successfully synthesized by a thermal bubble ejection assisted chemical-vapor-deposition and magnesiothermic reduction method. The morphology and structure of the as-prepared nanocomposites were characterized by field emission scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. When employed as anode materials in lithium ion batteries, C@Si@GF nanocomposites exhibited superior electrochemical per- formance including a high specific capacity of 1,200 mAh/g at the current density of 1A/g, excellent high rate capabilities and an outstanding cyclability. Post-mortem analyses identified that the morphology of 3D C@Si@GF electrodes after 200 cycles was well maintained. The synergistic effects arising from the combination of mesoporous Si nanospheres and graphene foam nanoarchitectures may address the intractable pulverization problem of Si electrode.     

Advanced rechargeable lithium-ion batteries based on bendable ZnCo2O4-urchins-on-carbon-fibers electrodes

A novel class of ZnCo₂O₄-urchins-on-carbon-fibers matrix has been designed, characterized, and used to fabricate high-performance energy storage devices. We obtained a reversible lithium storage capacity of 1180 mA·h/g even after 100 cycles, demonstrating the highreversible capacity and excellent cycle life of the as-prepared samples. Tested as fast-charging batteries, these electrodes exhibited a considerable capacity of 750 mA·h/g at an exceptionally high rate of 20 C (18 A/g), with an excellent cycle life (as long as 100 cycles), which are the best high-rate results reported at such a high charge/discharge current density for ZnCo₂O₄-based anode materials in lithium rechargeable batteries. Such attractive properties may be attributed to the unique structure of the binder-free ZnCo₂O₄-urchins-on-carbon-fibers matrix. Full batteries were also developed by combining the ZnCo₂O₄ anodes with commercial LiCoO₂ cathodes, which showed flexible/wearable and stable features for use as very promising future energy storage units.      

Composites of graphene and encapsulated silicon for practically viable high-performance lithium-ion batteries

A facile and scalable approach to synthesize silicon composite anodes has been developed by encapsulating Si particles via in situ polymerization and carbonization of phloroglucinol-formaldehyde gel, followed by incorporation of graphene nanoplatelets. As a result of its structural integrity, high packing density and an intimate electrical contact consolidated by the conductive networks, the composite anode yielded excellent electrochemical performance in terms of charge storage capability, cycling life and coulombic efficiency. A half cell achieved reversible capacities of 1,600 mAh·g^?1 and 1,000 mAh·g^?1 at 0.5 A·g^?1 and 2.1 A·g^?1, respectively, while retaining more than 70% of the initial capacities over 1,000 cycles. Complete lithium-ion pouch cells coupling the anode with a lithium metal oxide cathode demonstrated excellent cycling performance and energy output, representing significant advance in developing Si-based electrode for practical application in high-performance lithium-ion batteries.      

Graphene oxide-decorated Fe<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> microflowers as a promising anode for lithium and sodium storage

Mixed transition metal oxides (MTMOs) have received intensive attention as promising anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). In this work, we demonstrate a facile one-step water-bath method for the preparation of graphene oxide (GO) decorated Fe₂(MoO₄)₃ (FMO) microflower composite (FMO/GO), in which the FMO is constructed by numerous nanosheets. The resulting FMO/GO exhibits excellent electrochemical performances in both LIBs and SIBs. As the anode material for LIBs, the FMO/GO delivers a high capacity of 1,220 mAh·g^–1 at 200 mA·g^–1 after 50 cycles and a capacity of 685 mAh·g^–1 at a high current density of 10 A·g^–1. As the anode material for SIBs, the FMO/GO shows an initial discharge capacity of 571 mAh·g^–1 at 100 mA·g^–1, maintaining a discharge capacity of 307 mAh·g^–1 after 100 cycles. The promising performance is attributed to the good electrical transport from the intimate contact between FMO and graphene oxide. This work indicates that the FMO/GO composite is a promising anode for high-performance lithium and sodium storage.

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SnSb@carbon nanocable anchored on graphene sheets for sodium ion batteries

The development of materials with unique nanostructures is an effective strategy for the improvement of sodium storage in sodium ion batteries to achieve stable cycling performance and good rate capability. In this work, SnSbcore/carbon-shell nanocables directly anchored on graphene sheets (GS) were synthesized by the hydrothermal technique and chemical vapor deposition. The simultaneous carbon coating and the encapsulation of SnSb alloy is effective for alleviating the volume-change problem in sodium ion batteries. After optimizing the electrolyte for SnSb in the sodium ion batteries, the optimized coaxial SnSb/carbon nanocable/GS (SnSb/CNT@GS) nanostructure demonstrated stable cycling capability and rate performance in 1 M NaClO₄ with propylene carbonate (PC) + 5% fluoroethylene carbonate (FEC). The SnSb/CNT@GS electrode can retain a capacity of 360 mAh/g for up to 100 cycles, which is 71% of the theoretical capacity. This is higher than in the other three electrolytes tested (1 M NaClO₄ in PC, 1 M NaClO₄ in PC/FEC (1:1 v/v) and 1 M NaPF₆ + PC), and higher than that of the sample without the addition of graphene. The good electrochemical performance can be attributed to the efficient buffering provided by the outer carbon nanocable layer and the graphene inhibiting the agglomeration of SnSb particles, as well as its high conductivity.      

Multi-dimensionally ordered,multi-functionally integrated r-GO@TiO<Subscript>2</Subscript>(B)@Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> yolk–membrane–shell superstructures for ultrafast lithium storage

TiO₂(B) is an attractive new anode candidate for lithium-ion batteries (LIBs) due to its unique and highly desirable properties, including high structural integrity, long cycle life, and low cost. However, despite these merits, its inherent slow lithium and electron transport kinetics hinder its practical application to LIBs. Here, we propose a novel, simple route towards multi-dimensionally ordered, multi-functionally integrated reduced graphene oxide (r-GO)@TiO₂(B)@Mn₃O₄ yolk–membrane–shell superstructures in which r-GO nanosheets, TiO₂(B) nanosheets, and Mn₃O₄ nanoparticles are hierarchically organized to achieve remarkable synergistic interactions. This hybridization design is fundamentally bilateral in nature, aiming to overcome the conductivity and capacity deficiencies of TiO₂(B) simultaneously. The resulting r-GO@TiO₂(B)@Mn₃O₄ yolk–membrane–shell superstructures have great potential as advanced anode materials for ultrafast lithium storage, delivering a strikingly high reversible capacity of 662 mA·h·g^?1 at 500 mA·g^?1 after 500 charge–discharge cycles.

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Designed synthesis of ordered mesoporous graphene spheres from colloidal nanocrystals and their application as a platform for high-performance lithium-ion battery composite electrodes

Three-dimensional (3D) graphene has recently attracted enormous attention for electrochemical energy storage applications. However, current methods suffer from an inability to simultaneously control and engineer the porosity and morphology of the graphene frameworks. Here, we report the designed synthesis of ordered mesoporous graphene spheres (OMGSs) by transformation of self-assembled Fe₃O₄ nanocrystal superlattices. The resultant OMGSs have an ultrathin framework comprising few-layered graphene, with highly ordered and interconnected mesoporosity and a high surface area. These advantageous structural and textural features, in combination with the excellent electrical conductivity of the graphitic frameworks, render the OMGSs an ideal and general platform for creating hybrid materials that are well suited for use as composite electrodes in lithium-ion batteries (LIBs). As a proof-of-concept demonstration, SnO₂ and GeO₂ nanoparticles are incorporated into the OMGSs to afford SnO₂@OMGSs and GeO₂@OMGSs, respectively, both of which exhibit outstanding lithium storage properties when used as LIB anodes.

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Spin-coated silicon nanoparticle/graphene electrode as a binder-free anode for high-performance lithium-ion batteries

Si has been considered as a promising anode material but its practical application has been severely hindered due to poor cyclability caused by the large volume change during charge/discharge. A new and effective protocol has been developed to construct Si nanoparticle/graphene electrodes with a favorable structure to alleviate this problem. Starting from a stable suspension of Si nanoparticles and graphene oxide in ethanol, spin-coating can be used as a facile method to cast a spin-coated Si nanoparticle/graphene (SC-Si/G) film, in which graphene can act as both an efficient electronic conductor and effective binder with no need for other binders such as polyvinylidenefluoride (PVDF) or polytetrafluoroethylene (PTFE). The prepared SC-Si/G electrode can achieve a high-performance as an anode for lithium-ion batteries benefiting from the following advantages: i) the graphene enhances the electronic conductivity of Si nanoparticles and the void spaces between Si nanoparticles facilitate the lithium ion diffusion, ii) the flexible graphene and the void spaces can effectively cushion the volume expansion of Si nanoparticles. As a result, the binder-free electrode shows a high capacity of 1611 mA·h·g^?1 at 1 A·g^?1 after 200 cycles, a superior rate capability of 648 mA·h·g^?1 at 10 A·g^?1, and an excellent cycle life of 200 cycles with 74% capacity retention.      

Ultrathin MoS<Subscript>2</Subscript> with expanded interlayers supported on hierarchical polypyrrole-derived amorphous N-doped carbon tubular structures for high-performance Li/Na-ion batteries

Layered molybdenum disulfide (MoS₂) has received much attention as one of the most promising energy-storage and conversion materials for Li/Na ion batteries. Here, a simple and effective approach is proposed for the rational design and preparation of hierarchical three-d imensional (3D) amorphous N-doped carbon nanotube@MoS₂ nanosheets (3D-ANCNT@MoS₂) via a simple hydrothermal method, followed by an annealing process. With such a unique nanoarchitecture, ultrathin MoS₂ nanosheets grown on the external surfaces of polypyrrole-derived ANCNTs are assembled to form a hierarchical 3D nanoarchitecture, where the adopted ANCNTs serve not only as the template and continuous conductive matrix, but can also prevent MoS₂ from aggregating and restacking, and help to buffer the volumetric expansion of MoS₂ during cycling. More importantly, when evaluated as an anode material for lithium-ion batteries, the 3D-ANCNT@MoS₂ composite exhibits excellent cycling stability, superior rate performance, and reversible specific capacity as high as 893.4 mAh?g^-1 at 0.2 A?g^-1 after 200 cycles in a half battery, and 669.4 mAh?g^-1 at 0.2 A?g^-1 after 100 cycles in the 3D-ANCNT@MoS₂//LiCoO₂ full battery. With respect to sodium-ion batteries, the outstanding reversible capacity, excellent rate behavior, and good cycling performance of 3D-ANCNT@MoS₂ composites are also achieved.

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Construction of point-line-plane (0-1-2 dimensional) Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-SnO<Subscript>2</Subscript>/graphene hybrids as the anodes with excellent lithium storage capability

The assembly of hybrid nanomaterials has opened up a new direction for the construction of high-performance anodes for lithium-ion batteries (LIBs). In this work, we present a straightforward, eco-friendly, one-step hydrothermal protocol for the synthesis of a new type of Fe₂O₃-SnO₂/graphene hybrid, in which zero-dimensional (0D) SnO₂ nanoparticles with an average diameter of 8 nm and one-dimensional (1D) Fe₂O₃ nanorods with a length of ~150 nm are homogeneously attached onto two-dimensional (2D) reduced graphene oxide nanosheets, generating a unique point-line-plane (0D-1D-2D) architecture. The achieved Fe₂O₃-SnO₂/graphene exhibits a well-defined morphology, a uniform size, and good monodispersity. As anode materials for LIBs, the hybrids exhibit a remarkable reversible capacity of 1,530 mA·g^?1 at a current density of 100 mA·g^?1 after 200 cycles, as well as a high rate capability of 615 mAh·g^?1 at 2,000 mA·g^?1. Detailed characterizations reveal that the superior lithium-storage capacity and good cycle stability of the hybrids arise from their peculiar hybrid nanostructure and conductive graphene matrix, as well as the synergistic interaction among the components.

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Hollow TiO<Subscript>2–<Emphasis Type="Italic">X</Emphasis></Subscript> porous microspheres composed of well-crystalline nanocrystals for high-performance lithium-ion batteries

Hollow TiO_2–X porous microspheres consisted of numerous well-crystalline nanocrystals with superior structural integrity and robust hollow interior were synthesized by a facile sol-gel template-assisted approach and two-step carbonprotected calcination method, together with hydrogenation treatment. They exhibit a uniform diameter of ~470 nm with a thin porous wall shell of ~50 nm in thickness. The Brunauer-Emmett-Teller (BET) surface area and pore volume are ~19 m²/g and 0.07 cm³/g, respectively. These hollow TiO_2–X porous microspheres demonstrated excellent lithium storage performance with stable capacity retention for over 300 cycles (a high capacity of 151 mAh/g can be obtained up to 300 cycles at 1 C, retaining 81.6% of the initial capacity of 185 mAh/g) and enhanced rate capability even up to 10 C (222, 192, 121, and 92.1 mAh/g at current rates of 0.5, 1, 5, and 10 C, respectively). The intrinsic increased conductivity of the hydrogenated TiO₂ microspheres and their robust hollow structure beneficial for lithium ion-electron diffusion and mitigating the structural strain synergistically contribute to the remarkable improvements in their cycling stability and rate performance.

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纳米二氧化锡/三维大孔石墨烯复合电极的制备及其储锂性能的研究

以维生素C(VC)为还原剂,通过溶剂热还原法制备了纳米二氧化锡/三维大孔石墨烯复合负极材料(SnO_2/3DGr)。SEM和TEM测试表明,SnO_2/3DGr具有均匀分布的微米级孔隙,其中SnO_2晶粒尺寸为6~8nm,且均匀分布在石墨烯片层表面。电化学测试表明所制备的SnO_2/3DGr复合电极材料具有优异的电化学性能,该材料在电流密度为100mA/g时,循环100周之后仍然具有1678mAh/g的可逆比容量,在极高电流密度5A/g下,仍然保持405mAh/g的可逆比容量,表现出非常优异的循环稳定性和倍率性能。该材料独特的三维大孔结构以及SnO_2与石墨烯的协同作用,很好地抑制了SnO_2在循环过程中的体积效应,大大改善了SnO_2负极材料的电化学性能。     

A Robust and Conductive Black Tin Oxide Nanostructure Makes Efficient Lithium‐Ion Batteries Possible

SnO₂‐based lithium‐ion batteries have low cost and high energy density, but their capacity fades rapidly during lithiation/delithiation due to phase aggregation and cracking. These problems can be mitigated by using highly conducting black SnO_2?x , which homogenizes the redox reactions and stabilizes fine, fracture‐resistant Sn precipitates in the Li₂O matrix. Such fine Sn precipitates and their ample contact with Li₂O proliferate the reversible Sn → Li _x Sn → Sn → SnO₂/SnO_2?x cycle during charging/discharging. SnO_2?x electrode has a reversible capacity of 1340 mAh g^?1 and retains 590 mAh g^?1 after 100 cycles. The addition of highly conductive, well‐dispersed reduced graphene oxide further stabilizes and improves its performance, allowing 950 mAh g^?1 remaining after 100 cycles at 0.2 A g^?1 with 700 mAh g^?1 at 2.0 A g^?1. Conductivity‐directed microstructure development may offer a new approach to form advanced electrodes.     

锰氧化物/石墨烯复合材料作为锂离子电池负极的研究

以天然石墨为原料,采用改进的Hummers法合成含Mn的氧化石墨;400℃条件下氢气还原制备了锰氧化物/石墨烯复合材料。利用XRD、SEM和TEM对所制备的复合材料进行了表征。结果表明锰氧化物(MnOx)颗粒均匀地分布在石墨烯片层表面。将复合材料作为锂离子电池负极进行研究,在50mA/g电流密度下,首次库伦效率为70.4%,可逆容量达876mAh/g,并且具有良好的循环性能,在30次循环后仍保持在700mAh/g以上。     

In situ synthesis of SnO2 nanosheet/graphene composite as anode materials for lithium-ion batteries

A novel SnO₂/graphene composite has been synthesized via an in situ chemical synthesis method, in which single crystal SnO₂ nanosheets are uniformly grown on graphene support. The as-prepared products were characterized by X-ray diffraction, field emission scanning electron microscope, transmission electron microscope, Thermogravimetric analyses and Nitrogen adsorption/desorption. When used as an anode material for lithium ion batteries, the SnO₂/graphene composite exhibits an enhanced reversible lithium storage capacity and good cyclic performance. The first discharge and charge capacities are 1,366 and 975 mAh g^?1, respectively. After 100 cycles, the reversible discharge capacity is still maintained at 451 mAh g^?1 at the current densities of 100 mA g^?1, indicating that it’s a promising anode material for high performance lithium ion batteries.     

Carbon-supported and nanosheet-assembled vanadium oxide microspheres for stable lithium-ion battery anodes

Naturally abundant transition metal oxides with high theoretical capacity have attracted more attention than commercial graphite for use as anodes in lithium-ion batteries. Lithium-ion battery electrodes that exhibit excellent electrochemical performance can be efficiently achieved via three-dimensional (3D) architectures decorated with conductive polymers and carbon. As such, we developed 3D carbon-supported amorphous vanadium oxide microspheres and crystalline V₂O₃ microspheres via a facile solvothermal method. Both samples were assembled with ultrathin nanosheets, which consisted of uniformly distributed vanadium oxides and carbon. The formation processes were clearly revealed through a series of time-dependent experiments. These microspheres have numerous active reaction sites, high electronic conductivity, and excellent structural stability, which are all far superior to those of other lithium-ion battery anodes. More importantly, 95% of the second-cycle discharge capacity was retained after the amorphous microspheres were subjected to 7,000 cycles at a high rate of 2,000 mA/g. The crystalline microspheres also exhibited a high-rate and long-life performance, as evidenced by a 98% retention of the second-cycle discharge capacity after 9,000 cycles at a rate of 2,000 mA/g. Therefore, this facile solvothermal method as well as unique carbon-supported and nanosheet-assembled microspheres have significant potential for the synthesis of and use in, respectively, lithium-ion batteries.

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Confined growth of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanoparticles in nitrogen-doped mesoporous graphene fibers for high-performance lithium-ion battery anodes

Nanomaterials with electrochemical activity are always suffering from aggregations, particularly during the high-temperature synthesis processes, which will lead to decreased energy-storage performance. Here, hierarchically structured lithium titanate/nitrogen-doped porous graphene fiber nanocomposites were synthesized by using confined growth of Li₄Ti₅O₁₂ (LTO) nanoparticles in nitrogen-doped mesoporous graphene fibers (NPGF). NPGFs with uniform pore structure are used as templates for hosting LTO precursors, followed by high-temperature treatment at 800 °C under argon (Ar). LTO nanoparticles with size of several nanometers are successfully synthesized in the mesopores of NPGFs, forming nanostructured LTO/NPGF composite fibers. As an anode material for lithium-ion batteries, such nanocomposite architecture offers effective electron and ion transport, and robust structure. Such nanocomposites in the electrodes delivered a high reversible capacity (164 mAh·g^–1 at 0.3 C), excellent rate capability (102 mAh·g^–1 at 10 C), and long cycling stability.

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In situ synthesis of SnO2/graphene nanocomposite and their application as anode material for lithium ion battery

SnO₂/graphene nanocomposite was prepared via an in situ chemical synthesis method. The nanocomposite was characterized by X-ray diffraction, filed emission scanning electron microscope and transmission electron microscope, which revealed that tiny SnO₂ nanoparticles could be homogeneously distributed on the graphene matrix. The electrochemical performance of the SnO₂/graphene nanocomposite as anode material was measured by galvanostatic charge/discharge cycling. The SnO₂/graphene nanocomposite showed a reversible capacity of 665 mAh/g after 50 cycles and an excellent cycling performance for lithium ion battery, which was ascribed to the three-dimensional architecture of SnO₂/graphene nanocomposite. These results suggest that SnO₂/graphene nanocomposite would be a promising anode material for lithium ion battery.