SnS2纳米花/石墨烯纳米复合物的一步法合成及其增强的锂离子存储性能

SnS₂ is considered as an attractive anode material to substitute commercial graphite anodes of lithium-ion batteries due to its high specific capacity of 645 mAh·g^-1 as well as low cost. Nevertheless, it suffers poor large volume expansion during the lithiation/delithiation processes, leading to the loss of electrical contact and rapid capacity fading. Herein, by using a facile one-step solvothermal method, SnS₂ nanoflower/graphene nanocomposites (SnS₂ NF/GNs) were prepared, where flower-like SnS₂ hierarchical nanostructures consisting of ultrathin nanoplates, are tightly enwrapped in graphene nanosheets. As anode materials for lithium-ion batteries, the SnS₂ NF/GNs electrode exhibit superior electrochemical performance, with a reversible capacity of 523 mAh·g^-1 after 200 charge-discharge cycles. The enhanced Li storage performance was attributed to the synergistic effect of SnS₂ and graphene. The SnS₂ NF can effectively accommodate the volume change and shorten Li⁺ diffusion distance, while graphene nanosheets can further alleviate the volume expansion of SnS₂ and improve the electronic conductivity.     

Enhanced Anode Performances of Polyaniline-TiO(2)-Reduced Graphene Oxide Nanocomposites for Lithium Ion Batteries

Here, we report a three-layer-structured hybrid nanostructure consisting of transition metal oxide TiO(2) nanoparticles sandwiched between carbonaceous polymer polyaniline (PANI) and graphene nanosheets (termed as PTG), which, by simultaneously hindering the agglomeration of TiO(2) nanoparticles and enhancing the conductivity of PTG electrode, enables fast discharge and charge. It was demonstrated that the PTG exhibited improved electrochemical performance compared to pure TiO(2). As a result, PTG nanocomposite is a promising anode material for highly efficient lithium ion batteries (LIBs) with fast charge/discharge rate and high enhanced cycling performance [discharge capacity of 149.8 mAh/g accompanying Coulombic efficiency of 99.19% at a current density of 5C (1000 mA/g) after 100 cycles] compared to pure TiO(2). We can conclude that the concept of applying three-layer-structured graphene-based nanocomposite to electrode in LIBs may open a new area of research for the development of practical transition-metal oxide graphene-based electrodes which will be important to the progress of the LIBs science and technology.     

Synthesis of SnS2 Ultrathin Nanosheets as Anode Materials for Potassium Ion Batteries

Potassium(K)ion batteries present their promising application for large-scale energy storage systems with cost-effective characteristic.Unfortunately,the large K ion radius results in sluggish K ion diffusion kinetics and volume expansion of the electrode during the K ion insertion/extraction process.It is a challenge to explore capable anode materials with remarkable K ion storage ability.Herein,we design and prepare SnS2 ultrathin nanosheets via a facile hydrothermal process.When severing as anode materials for K ion batteries with optimized electrolyte,SnS2 presents an improved capacity and rate ability.The capable electrochemical performance is ascribed to the reduced ion diffusion pathway and capacitor-dominated K-ion storage process.In addition,the K ion storage mechanism of SnS2 is investigated by the ex-situ X-ray diffraction technique.     

Controlling the morphology,size and phase of Nb2O5 crystals for high electrochemical performance

Herein, the nano-sized niobium pentoxide (Nb₂O₅) with different morphologies and phase structures are synthesized through a very simple thermal treatment method, including the pseudohexagonal Nb₂O₅ nanosheets and pseudohexagonal Nb₂O₅ nanoparticles, orthorhombic Nb₂O₅ nanoparticles. The synthesized pseudohexagonal Nb₂O₅ nanosheets and orthorhombic Nb₂O₅ nanoparticles exhibit better cycling and rate performance than the pseudohexagonal Nb₂O₅ nanoparticles due to the different morphologies and phase structures.     

多壁纳米碳管约束二硫化锡作为锂离子电池负极的电化学行为

通过两步法制备多壁纳米碳管约束SnS_2纳米材料(SnS_2@MWCNT)。采用直流电弧等离子体法在甲烷气氛下制备多壁纳米碳管约束金属锡纳米结构(Sn@MWCNT)作为前驱体,再通过硫化反应获得SnS_2@MWCNT纳米结构。对材料进行Raman、X射线衍射(XRD)、透射电镜(TEM)等物理表征的结果显示多壁纳米碳管长约400nm,表面碳层晶化程度良好,碳层厚度约10 nm。以Sn S2@MWCNT纳米结构作为负极材料的锂离子电池显示出较为良好的电化学性能。其首次充放电库伦效率为71%,循环50次后,容量仍保持703 mAh?g~(-1)。SnS_2@MWCNT纳米结构电极的高容量特性源于多种活性物质共同提供容量,且各物质反应平台不同。平台呈现明显阶梯型,缓解了体积膨胀效应对电极材料的破坏。     

镶嵌于NH2-MIL-125 (Ti)衍生氮掺多孔碳中的花状超细纳米TiO2作为高活性和稳定性的锂离子电池负极材料

由于具有高安全性和优异的循环稳定性,二氧化钛(TiO₂)作为负极材料被广泛地应用于锂离子电池领域。但是较差的导电性和离子传输速率限制了TiO₂的进一步应用和发展。鉴于此,我们以花状NH₂-MIL-125 (Ti)为前驱体和硬模板,成功合成出了具有花状结构的超细纳米TiO₂/多孔氮掺杂碳片(N-doped porous carbon)复合物(记为FL-TiO₂/NPC)。过程中所制备的纳米TiO₂-金属有机构架(Ti-MOF)展现出由二维褶皱多孔纳米片堆积、组装而成的花状结构。一方面,二维褶皱纳米片包含TiO₂纳米颗粒可以增大活性物质与电解液的接触面积;另一方面,氮掺杂多孔碳基体可以提高整体复合物的导电性和结构完整性。将所获得的FL-TiO₂/NPC作为负极组装成的锂半电池, 在0.5 A·g^-1、300圈后仍有384.2 mAh·g^-1以及在1 A·g^-1、500圈仍有279.1 mAh·g^-1的比容量。进一步性能测试表明,在2 A·g^-1、2000圈长循环测试后,其仍能保持256.5 mAh·g^-1的比容量和接近100%的库伦效率。该优异的电化学活性和稳定性主要起源于材料独特的花状结构。我们的合成策略为今后制备高储锂性能的金属氧化物/多孔氮掺杂碳负极提供了一种新的思路。     

Fabrication of Nb2O5/C nanocomposites as a high performance anode for lithium ion battery

Nb₂O₅/C nanosheets are successfully prepared through a mixing process and followed by heating treatment.Such Nb₂O₅/C based electrode exhibits high rate performance and remarkable cycling ability, showing a high and stable specific capacity of ~380 mAh g^-1 at the current density of 50 mA g^-1(much higher than the theoretical capacity of Nb₂O₅).Further more,at a current density of 500 mA g^-1,the nanocomposites electrode still exhibits a specific capacity of above 150 mAh g^-1 after 100 cycles.These results suggest the Nb₂O₅/C nanocomposite is a high performance anode material for lithium-ion batteries.     

基于水凝胶衍生的硅/碳纳米管/石墨烯纳米复合材料及储锂性能

通过氧化石墨烯(GO)和壳聚糖(Cs)之间的氢键以及静电作用形成GO水凝胶,从而将纳米硅颗粒和碳纳米管(CNT)原位包封于其中,再经冷冻干燥及随后的热处理制得三维硅/碳纳米管/石墨烯(Si-CNT@G)纳米复合材料。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)、热重分析(TGA)等技术对制得样品的物相、结构和微观形貌等进行了表征。结果表明,所得复合材料在CNT纵横交织的石墨烯网络中,均匀地分布着纳米硅颗粒。当作为锂离子电池的负极材料时,在两种碳介质的协同作用下,有效缓冲硅材料在充放电过程中脱/嵌锂引起的体积变化,缩短了锂离子和电子传输的距离,Si-CNT@G复合材料表现出较好的循环稳定性以及倍率性能。在500 m A·g~(-1)的充放电电流密度下,经过200圈循环后,其放电比容量仍高达673.7 m Ah·g~(-1),容量保持率高达97%;即使将充放电电流密度升至2000 m A·g~(-1)时,该复合材料仍保持有566.9 m Ah·g~(-1)的高可逆放电比容量。独特的制备方法和优越的储锂性能,使得Si-CNT@G纳米复合材料成为理想的高性能锂离子电池负极材料的候选.     

层状钒青铜纳米片的制备及其锂离子电池阳极材料性能

室温下, 在水溶液中将铵根离子和水分子插入到商用V₂O₅纳米颗粒的层间, 制得了层状的钒青 铜[(NH₄)₂V₆O₁₆·H₂O]纳米片. 该纳米片的尺寸为2~10 μm, 厚度为50~250 nm. 与商用V₂O₅纳米颗粒相比, (NH₄)₂V₆O₁₆·H₂O纳米片用作锂离子电池(LIBs)的阳极材料时, 其性能得到较大提升, 包括大的可逆放电容量 (0.1 A/g时为1148 mA·h/g)、 出色的循环性能(循环70圈后在0.1 A/g时具有1002 mA·h/g的高容量)和高倍率性能(在0.1 A/g时具有1070 mA·h/g的可逆性能). 研究结果表明, (NH₄)₂V₆O₁₆·H₂O纳米片可以作为锂离子电池优良的阳极材料, 也有望应用于其它(如钠离子电池和锌离子电池等)可再充电电池.     

High reversible capacity and rate capability of ZnCo2O4/graphene nanocomposite anode for high performance lithium ion batteries

A facile and straightforward method was adopted to synthesize ZnCo₂O₄/graphene nanocomposite anode. In the first step, pure ZnCo₂O₄ nanoparticles were synthesized using urea-assisted auto-combustion synthesis followed by annealing at a low temperature of 400 °C. In the second step, in order to synthesize ZnCo₂O₄/graphene nanocomposite, the obtained pure ZnCo₂O₄ nanoparticles were milled with 10 wt% reduced graphene nanosheets using high energy spex mill for 30 s. The ZnCo₂O₄ nanoparticles, with particle sizes of 25–50 nm, were uniformly dispersed and anchored on the reduced graphene nanosheets. Compared with pure ZnCo₂O₄ nanoparticles anode, significant improvements in the electrochemical performance of the nanocomposite anode were obtained. The resulting nanocomposite delivered a reversible capacity of 1124.8 mAh g⁻¹ at 0.1 C after 90 cycles with 98% Coulombic efficiency and high rate capability of 515.9 mAh g⁻¹ at 4.5 C, thus exhibiting one of the best lithium storage properties among the reported ZnCo₂O₄ anodes. The significant enhancement of the electrochemical performance of the nanocomposite anode could be credited to the strong synergy between ZnCo₂O₄ and graphene nanosheets, which maintain excellent electronic contact and accommodate the large volume changes during the lithiation/delithiation process.     

Freeze-drying-assisted Synthesis of Mesoporous CoMoO4 Nanosheets as Anode Electrode Material for Enhanced Lithium Batteries

A facile and green freeze-drying-assisted method was proposed to synthesize C0MoO4 mesoporous nano-sheets(MPNSs).The resulting product exhibits a Mgh specific capacity and good rate perfomance when evalimte an anode material for lithium-ion batteries(LIBs).The reversible specific capacity can be kept at 1105.2 mA·h·g^-1 after 100 cycles at a current density of 0.2 A/g.Even at the current densities of 1 and 4 A/gs the CoMoO4 MPNSs electrode can still retain the reversible capacities of 1148.7 and 540 mA·h·g^-1,respectively.Furthermore,the full cell(LiPePO4 catliode/CoMoO4 MPNSs anode)displays a stable discharge capacity of 146.7 mA·h·g^-1 at 0.1 C(1 C=170 mA/g)together with an initial coulombic efficiency of 98.2%.In addition,the CoMoO4 crystal structure is destroyed and reduced into Co^0 and Mo^0 in the first discharge process.In the subsequent cycles,the attractive Li storage properties come from the reversible conversions between Co/Co^2+and Mo/Mo^6+.The improved electroche-mical performance of CoMoO4 MPNSs is mainly attributed to their unique porous structures,which not only possess a good ion diffusion and electronic conduction pathway,but also provide many cavities to alleviate the volume changes during repeated cycling.This work offers a new perspective to the design of other porous electrode materials with a good energy storage performance.     

Porous bowl-shaped VS_2 nanosheets/graphene composite for high-rate lithium-ion storage

Two-dimensional (2D) layered vanadium disulfide (VS_2) is a promising anode material for lithium ion batteries (LIBs) due to the high theoretical capacity.However,it remains a challenge to synthesize monodispersed ultrathin VS_2 nanosheets to realize the full potential.Herein,a novel solvothermal method has been developed to prepare the monodispersed bowl-shaped NH_3-inserted VS_2 nanosheets (VS_2).The formation of such a unique structure is caused by the blocked growth of (001) or (002) crystal planes in combination with a ripening process driven by the thermodynamics.The annealing treatment in Ar/H_2creates porous monodispersed VS_2(H-VS_2),which is subsequently integrated with graphene oxide to form porous monodispersed H-VS_2/rGO composite coupled with a reduction process.As an anode material for LIBs,H-VS_2/rGO delivers superior rate performance and longer cycle stability:a high average capacity of 868/525 mAh g~(-1) at a current density of 1/10 A g~(-1);a reversible capacity of 1177/889 mAh g~(-1) after 150/500 cycles at 0.2/1 A g~(-1).Such excellent electrochemical performance may be attributed to the increased active sites available for lithium storage,the alleviated volume variations and the shortened Li-ion diffusion induced from the porous structure with large specific surface area,as well as the protective effect from graphene nanosheets.     

Design and Preparation of Graphene/Fe2O3 Nanocomposite as Negative Material for Supercapacitor

The development of high specific capacitance electrode materials with high efficiency, scalability and economic feasibility is significant for the application of supercapacitors, however, the synthesis of electrode material still faces huge challenges. Herein, graphene(G)/Fe₂O₃ nanocomposite was prepared via a simple hydrothermal method connected with subsequent thermal reduction process. Scanning electron microscopy(SEM) and transmission electron microscopy(TEM) results showed rod-like Fe₂O₃ nanoparticles were prepared and well-dispersed on graphene layers, providing a rich active site and effectively buffering the aggregation of Fe₂O₃ nanoparticles in the process of electrochemical reaction. The specific capacitance of the obtained G/Fe₂O₃ nanocomposite as negative electrode for supercapacitor was 378.7 F/g at the current density of 1.5 A/g, and the specific capacitance retention was 88.76% after 3000 cycles. Furthermore, the asymmetric supercapacitor(ASC) was fabricated with G/Fe₂O₃ nanocomposite as negative electrode, graphene as positive electrode, which achieved a high energy density of 64.09 W∙h/kg at a power density of 800.01 W/kg, maintained 30.07 W∙h/kg at a power density of 8004.89 W/kg, and retained its initial capacitance by 78.04% after 3000 cycles. The excellent result offered a promising way for the G/Fe₂O₃ nanocomposite to be applied in high energy density storage systems.     

One-step construction of MoO_2 uniform nanoparticles on graphene with enhanced lithium storage

Transition-metal oxides are considered to be a promising anode material for lithium-ion batteries(LIBs)due to their high capacities,low cost,and ease of synthesis.Herein,a hybrid nanosheet composed of uniform MoO_2 nanoparticles(NPs) homogeneously immobilized on the reduced graphene oxide nanosheets(MoO_2 NP@rGO) is first synthesized by a self-templating and subsequent calcination treatment.The unique two-dimensional hybridnanosheets provides several merits.rGO can be used as a favorable support for the loading of electrochemically active MoO_2 NPs.Meanwhile,MoO_2 NPs can effectively prevent the stacking of the rGO.The effective combination of MoO_2 NPs and rGO nanosheets furnish additional electrochemically interfacial active sites for extra lithium ion sto rage.Noticeably,the as-fabricated hybrid nanosheets deliver a reversible capacity of 641 mAh/g after 350 cycles at a current density of 1000 mA/g with a good rate capability.The greatly enhanced lithium storage properties of MoO_2 NP@rGO indicate the importance of elaborate construction of novel hybrid hierarchical structures.     

Synthesis and Electrochemical Performance of Co3O4/Graphene

Co3O4/reduced graphene oxide composites were synthesized via a simple electrochemical method from graphene oxide and Co（NO3）2·6H2O as raw materials.Co3O4 nanoparticles with sizes of around 30-50 nm were distributed on the surface of graphene nanosheets confirmed by scanning electron microscopy and transmission electron microscopy.Electrochemical properties of Co3O4/graphene composite were tested by cyclic voltammetry,galvanostatic charge-discharge,and electrochemical impedance spectroscopy.The Co3O4/reduced graphene oxide composite was used as the pseudocapacitor electrode in the 2 mol/L NaOH aqueous electrolyte solution.The Co3O4/reduced graphene oxide composite electrode exhibited a specific capacitance of 357 F/g at a current density of 0.5 A/g in a three-electrode system.72％ of capacitance was retained when the current density increased to 3 A/g.The Co3O4/reduced graphene oxide composite prepared electrodes show a high rate capability and excellent long-term stability.After 1000 cycles of charge and discharge,the capacitance is still maintained 87％ at a current density of 1 A/g,indicating that the composite is a oromising alternative electrode material used for supercapacitors.     

硫掺杂二氧化钛/碳化钛复合材料的制备及储锂性能

通过二维层状Ti_3C_2的原位水热氧化和气相硫化反应,制备了硫掺杂二氧化钛/碳化钛(S-TiO_2/Ti_3C_2)复合材料,并用于电化学储锂。结果表明,二氧化钛纳米颗粒原位生长在碳化钛片层上,且硫成功掺杂到二氧化钛中。这种S-TiO_2/Ti_3C_2复合结构作为锂离子电池的负极材料,表现出较好的电化学性能。在0.2 A/g的电流密度下循环100圈后,放电比容量稳定在288 m A·h/g,远高于纯Ti_3C_2和TiO_2/Ti_3C_2电极的放电比容量。S-TiO_2/Ti_3C_2复合材料表现出的较高比容量和良好的循环性能,主要归因于复合材料的特殊纳米结构优势:二氧化钛原位生长在碳化钛上,使复合材料具有稳定良好的接触界面,能够促进电子的快速转移,同时可以有效避免循环过程中两种组分的分离;硫在二氧化钛中的掺杂可以提高二氧化钛的导电性,并引入缺陷,提高反应活性。此研究工作为二维材料的原位转化及复合提供了新的思路和研究方法。     

Controllable deposition of a platinum nanoparticle ensemble on a polyaniline/graphene hybrid as a novel electrode material for electrochemical sensing

We demonstrate for the first time an interfacial polymerization method for the synthesis of high-quality polyaniline-modified graphene nanosheets (PANI/GNs), which represents a novel type of graphene/polymer heterostructure. The interfacial polymerization at a liquid-liquid interface allows PANI to grow uniformly on the surface of the GNs. An ultra-high loading of Pt nanoparticles was then controllably deposited on the surface of the PANI/GNs to form a Pt/PANI/GNs hybrid. The obtained composites were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The Pt/PANI/GNs hybrid shows excellent electrocatalytic activity toward methanol oxidation and oxygen reduction. H(2)O(2) and glucose were used as two representative analytes to demonstrate the sensing performance of a Pt/PANI/GNs-modified electrode. It is found that this sensing element shows high sensitivity and a low detection limit for H(2)O(2) and glucose. The results demonstrate that the Pt/PANI/GNs hybrid may be an attractive and advanced electrode material with potential applications in the construction of electrochemical sensors and biosensors.     

From Amorphous Carbon to Carbon Nanobelts and Vertically Oriented Graphene Nanosheets Synthesized by Plasma-enhanced Chemical Vapor Deposition

Carbon materials with various structures were produced via plasma-enhanced chemical vapor deposition by controlling substrate temperature and mixed gases in the atmosphere. Scanning electron microscopy(SEM), transmission electron microscopy(TEM), high resolution transmission electron microscopy(HRTEM) and Raman spectroscopy were employed to investigate the morphology and structure of the materials. The results show that at a low substrate temperature(100 ℃) in CH₄:Ar(flow rate ratio was 100 cm³/min:10 cm³/min), amorphous carbon formed on Si(100) that could act as a support for the growth of carbon nanobelt and layer graphene at 800 ℃. Vertically oriented multi-layer graphene nanosheets(GNs) were catalyst-free synthesized on Si and Ni foam at 800 ℃ in a mixture of CH₄:Ar(20 cm³/min:60, 80 and 100 cm³/min). The capacitor character investigated by cyclic voltammetry and galvanostatic charge/discharge indicates that for the as-synthesized GNs, the electrochemical capacitance is very small(16 F/g at current density of 16 A/g). However, having been treated in acidic solution, the GNs exhibited good capacitive behavior, with a capacitance of 166 F/g, and after 800 charge/discharge cycles at 32 A/g, the capacitance could retain about 88.4%. The enhancement of specific capacitance is attributed to the increase of specific surface area after etching treatment of them.     

Flower-like Cu5Sn2S7/ZnS nanocomposite for high performance supercapacitor

Due to the synergistic effect between ZnS and Cu₅Sn₂S₇, the ZnS can enhance electrochemical performance of pristine Cu₅Sn₂S₇.     

Controllable synthesis, magnetism and solubility enhancement of graphene nanosheets/magnetite hybrid material by covalent bonding

Hybrids of Fe(3)O(4) nanoparticles and surface-modified graphene nanosheets (GNs) were synthesized by a two-step process. First, graphene nanosheets were modified by SOCl(2) and 4-aminophenoxyphthalonitrile to introduce nitrile groups on their surface. Second, the nitrile groups of surface-modified graphene nanosheets were reacted with ferric ions on the surface of Fe(3)O(4) with the help of relatively high boiling point solvent ethylene glycol to form a GNs/Fe(3)O(4) hybrid. The covalent attachment of Fe(3)O(4) nanoparticles on the graphene nanosheet surface was confirmed by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), energy-dispersive X-ray spectrometer (EDS) and scanning electron microscopy (SEM). TEM and HRTEM observations indicated that the sizes of the nanoparticles and their coverage density on GNs could be easily controlled by changing the concentration of the precursor and the weight ratio to GNs. Magnetic measurements showed that magnetization of the hybrid materials is strongly influenced by the reaction conditions. Chemically bonded by phthalocyanine, the solubility of as-synthesized GNs/Fe(3)O(4) hybrid materials was greatly enhanced, which was believed to have potential for applications in the fields of composites, wastewater treatment and biomaterials.