Embedding Co3O4 nanoparticles into graphene nanoscrolls as anode for lithium ion batteries with superior capacity and outstanding cycling stability

Co_3O_4 is a promising high-performance anode for lithium ion batteries(LIBs), but suffers from unsatisfied cyclability originating duo to low electrical conductivity and large volume expansion during charge and discharge process. Herein, we successfully constructed the Co_3O_4 nanoparticles embedded into graphene nanoscrolls(GNSs) as advanced anode for high-performance LIBs with large capacity and exceptional cyclability. The onedimensional(1 D) Co_3O_4/GNSs were synthesized via liquid nitrogen cold quenching of large-size graphene oxide nanosheets and sodium citrate(SC) modified Co_3O_4 nanoparticles, followed by freeze drying and annealing at400 °C for 2 h in nitrogen atmosphere. Benefiting from the interconnected porous network constructed by 1 D Co_3O_4/GNSs for fast electron transfer and rapid ion diffusion, and wrinkled graphene shell for significantly alleviating the huge volume expansion of Co_3O_4 during lithiation and delithiation. The resultant Co_3O_4/GNSs exhibited ultrahigh reversible capacity of 1200 mAh g~(-1) at 0.1 C, outperforming most reported Co_3O_4 anodes.Moreover, they showed high rate capability of 600 m Ah g-1 at 5 C, and outstanding cycling stability with a high capacity retention of 90% after 500 cycles. Therefore, this developed strategy could be extended as an universal and scalable approach for intergrating various metal oxide materials into GNSs for energy storage and conversion applications.     

Pt-induced electrochemical growth of ZnO rods onto reduced graphene oxide for enhanced photodegradation performance

Photodegradation of organic pollutants over semiconductor catalysts is considered to be a viable method for wastewater treatment.Of the different semiconductor photocatalysts,ZnO has been widely used for the photodegradation of organic pollutants.Meanwhile,graphene is being actively investigated as a cocatalyst for such processes.The high carrier transport rate of graphene can favor the transfer of photoexcited electrons,while the increased specific surface area provides adsorption sites for the organic effluent molecules,thereby improving overall photocatalytic activity.Therefore,in this study,Pt–ZnO–reduced graphene oxide(RGO)rods with different RGO contents are synthesize during a novel Pt-induced electrochemical method,where ZnjZnO acts as the anode and PtjH2OjH2acts as the cathode.The photocatalytic degradation activity of the Pt–ZnO–RGO rods is remarkably improved under UV–visible light irradiation,with the optimum loading RGO content of 1 wt%.     

Influence of graphene microstructures on electrochemical performance for supercapacitors

The influence of variant graphenes on electrochemical performance for supercapacitors was studied comparatively and systematically by using SEM, FTIR and Raman spectroscopy, cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). The results revealed that: 1) the nitrogen-doped graphene (N-G) electrode exhibited the highest specific capacitance at the same voltage scan rate; 2) the specific capacitance of the N-G reached up to 243.5 F/g at 1 A/g, while regular graphite oxide (GO) was 43.5 F/g and reduced graphene oxide (rGO) was 67.9 F/g; 3) N-G exhibited the best supercapacitance performance and the superior electrochemical properties, which made it an ideal electrode material for supercapacitors.     

轻度剥离二硫化钼／石墨烯复合材料的制备及其电化学储锂性能

为了增强MoS2的电化学储锂性能,将轻度剥离的商业MoS2与氧化石墨烯悬浮液混合,用液相还原法制备了轻度剥离MoS2／石墨烯复合材料,并对其微观结构和形貌进行了表征。结果表明轻度剥离MoS2的层数明显减少,其表面产生了许多裂纹,复合材料中轻度剥离的MoS2与石墨烯能较好地复合在一起。电化学测试表明与商业化MoS2比,轻度剥离MoSe／石墨烯复合材料具有更高的电化学储锂容量（1022mAh／g）,更好的循环稳定性能和显著增强的充放电倍率性能。电化学阻抗测试表明石墨烯显著降低了电极反应过程中的电子转移电阻。电化学储锂性能的增强主要是由于轻度剥离MoS2层数的明显减少及其表面的许多裂纹,以及轻度剥离MoS2与石墨烯之间的相互协同作用。电化学阻抗测试证明了石墨烯显著增强了复合电极材料的导电性能和电化学贮锂过程中电子传递能力。     

Annealing temperature-dependent electrochemical properties of Aeroxide P25 TiO_2 nanoparticles as anode material for lithium storage

TiO_2 has been widely studied as an important electrode material for electrochemical energy storage.Understanding its relationship between textural properties and electrochemical characteristics is essential to boosting its practical performances. Herein, Aeroxide P25 TiO_2 nanoparticles annealing at different temperatures(400–600 °C) were investigated as an anode material of lithium ion battery. Their evolution in crystal phase and microstructural characteristics were characterized by XRD and BET surface analysis, and their lithium storage properties in half-cells were evaluated by various electrochemical analyses, including cyclic voltammetry, cycling testing, and electrochemical impedance spectroscopy. It was found that the lithium storage properties were critically dependent on the size of TiO_2 anode materials. Pristine P25 initially exhibited the highest initial discharge specific capacity due to its smallest particle size; however, rapid capacity loss occurred during extended cycling. The annealing process was found to effectively enhance the cycling stability of TiO_2 although possessing a large particle size and smaller surface area. Typically, P400 showed the best performances in cycling stability, capacity retention ratio, and rate capability, which is mainly attributed to the synergistic effect of high crystallinity, reasonable particle size, and less internal resistance. This study provides an instance of optimizing the textural properties of metal oxides for advanced LIB anode material applications.     

Graphene-wrapped Fe2O3 nanorings for Li ion battery anodes

Graphene-wrapped Fe2O3 nanorings （RGO/ Fe2O3） were synthesized by a facile approach, which assembled with graphene and the Fe2O3 nanorings pre- cursor through the colloidal coagulation effect at room temperature. The uniform Fe2O3 nanorings prepared by hydrothermal routes were homogeneously distributed and well wrapped by graphene. When tested as anode for lithium ion batteries, RGO/Fe2O3 exhibits a high capacity and good cycling stability. This could be attributed to the interaction of ring-shaped structure and graphene sheets, which inherit the good kinetic property of Fe2O3 nanorings and enhance the structural integrity with graphene sheets＇ support.     

A review on recent progress of non-stoichiometric SiOx anodes based on lithium ion batteries

SiO_x anode has attracted more and more attention due to its rich reserves and high theoretical capacity. However,the disadvantages of low initial Coulombic efficiency and large volume change limit its application. Therefore in this review, the research progress of SiO_x anode will be summarized in detailed to demonstrate the various strategies adopted by researchers. Systematically introduction of the progress on preparation methods and modification strategies would be discu...     

A ternary FeS_2/Fe_7S_8@nitrogen-sulfur co-doping reduced graphene oxide hybrid towards superior-performance lithium storage

Iron sulfides are promising anode materials for lithium ion batteries(LIBs) owe to their high theoretical capacity and low cost. However, unsatisfactory electronic conductivity, dissolution of polysulfides, and severe agglomeration during the cycling process limit their applications. To solve these issues, a ternary FeS₂/Fe₇S₈@nitrogensulfur co-doping reduced graphene oxide hybrid(FeS₂/Fe₇S₈@NSG) was designed and synthesized throu...     

A fluid dynamics route for producing graphene and its analogues

A novel fluid dynamics route for scalable and efficient production of graphene and its analogues is demonstrated. Atomic force microscopy and transmission electron microscopy analyses strongly suggest that the bulk layered materials （graphite, BN, MoS2, and WS2） are efficiently exfoliated into individual layers containing mono-and few-layer nanosheets. Computational fluid dynamics analysis indicates that multiple fluid dynamics events are responsible for efficient exfoliation. Cavitation and pressure release can generate normal force for exfoli- ation. The velocity gradient-induced viscous shear stress, the turbulence-induced Reynolds shear stress, and shear effects stemmed from turbulence and flow channel-induced collisions can generate lateral force for exfoliation, resulting in theses bulk layered materials self-exfoliation down to single or few layers through their intrinsically lateral self-lubricating ability.     

Facile synthesis of CoFe2O4 nanoparticles anchored on graphene sheets for enhanced performance of lithium ion battery

Recently, metal oxides as high capacity anode materials had been investigated for lithium ion batteries.However, the fast capacity fading upon cycling leaded poor durability, which hindered their application as higher energy density of lithium ion battery. In this paper, a nanostructured nanocomposite with graphene supported CoFe_2O_4 nanoparticles(NPs) was prepared via simple hydrothermal reaction. The uniform CoFe_2O_4 NPs were anchored on graphene sheets, which brought a good performance on cyclability. Combined with the optimization of graphene content, the anode delivered a better capacity retention of 944 m A h g~(-1)over 50 cycles at current density of 100 m A g~(-1)and the good reversible capacity as 990 m A h g~(-1)when the rate returned from 5 A g~(-1)to 0.1 A g~(-1)after 60 cycles. The present work provided a desired structure for conversion anode materials or other electrode materials of large volume change.     

MnO/石墨烯复合材料的制备及其作为锂离子电池负极的研究

通过原位复合方法合成碳包覆MnO/石墨烯(C@MnO/GN)复合材料并探究其作为锂离子电池负极材料的电化学性能.扫描电子显微镜(SEM)以及透射电子显微镜(TEM)表征结果表明,MnO纳米颗粒(直径约为30~50nm)均匀分散在石墨烯片层上,且颗粒外面包裹一层厚度约为5nm的碳层.电化学测试结果表明该材料作为锂离子电池负极具有优异的倍率和循环性能.0.2和0.5A/g电流密度下,比容量分别为800和700mAh/g;10A/g电流密度下比容量仍能保持在372mAh/g;当电流密度调回0.5A/g时,其比容量仍能恢复到730mAh/g.该材料也表现出优异的循环性能,在5和10A/g电流密度下依次循环100圈,容量保持率几乎100%.     

PLD制备LiMn2O4薄膜及参数对薄膜微观结构的影响

用脉冲激光沉积（PLD）,分别在不锈钢和单晶硅（111）衬底上生长了LiMn2O4薄膜,并对所生长LiMn2O4薄膜的结构进行了研究。结果发现,生长在不锈钢衬底上的薄膜具有粗糙的表面和随机的结晶取向,生长在单晶硅衬底上的薄膜具有相对光滑的表面,并具有明显的（111）方向上的择优取向。还研究了脉冲频率和总脉冲数对薄膜生长的影响,结果显示,在相同的沉积条件下,对于不同衬底,LiMn2O4薄膜的生长率不同;脉冲频率对薄膜生长的影响明显,在相同总脉冲数情况下,脉冲频率大,薄膜生长率明显增大。     

Nanostructured LiMn2O4 and their composites as high-performance cathodes for lithium-ion batteries

Improvement of the energy density and power density of the lithium-ion batteries is urgently required with the rapid development of electric vehicles and portable electronic devices. The spinel LiMn2O4 is one of the most promising cathode materials due to its low cost, nontoxicity, and improved safety compared with commercial LiCoO2. Developing nanostructured electrode materials represents one of the most attractive strategies to dramatically enhance battery performance, such as capacity, rate capability and cycling life. Currently, extensive efforts have been devoted to developing nanostructured LiMn2O4 and LiMn2O4/carbon nanocomposites to further improve the rate capability of lithium-ion batteries for high-power applications. In this paper, recent progress in developing nanostructured LiMn2O4 and LiMn2O4/carbon nanocomposites is reviewed, and the benefits to the electrochemical performance of LiMn2O4-based cathodes by using these electrode materials are also discussed.     

锂离子电池锡氧化物基负极材料的软化学合成

采用新兴的软化学方法合成了锡氧化物基粉末材料.用X-射线衍射、扫描电镜和电化学方法对材料的微观结构、形貌和电化学性能进行了研究.结果表明：锡氧化物基材料的颗粒的平均粒径约为200 nm,颗粒之间形成了类似中孔材料的相互连接的网状结构.这种材料的可逆充电容量超过570 mAh/g,30次循环后平均每次循环的容量衰减只有0.15%.良好的电化学性能表明锡氧化物基材料有望作为新一代锂离子电池的负极材料.     

Functionalization of graphene materials by heteroatom-doping for energy conversion and storage

Recent development in nanoscience and nanotechnology has opened up new frontiers in materials science and engineering to create new materials for energy generation and storage. Owing to their earth abundance, low-cost, structural tunability, large-surface area, and unique physicochemical properties, graphitic carbon materials have attracted a great deal of attention for energy-related applications. However, the pristine graphene materials without functionalization is intractable (insoluble and infusible), which has hindered their practical applications. Therefore, considerable research effort has been devoted to the development of functionalized graphene materials with desirable properties for specific applications, including energy conversion and storage. It was demonstrated that functionalized graphene materials with tunable work functions were useful as charge-extraction materials to effectively improve solar cell performance while those with high electrocatalytic activities could be used as metal-free catalysts in fuel cells, metal-air batteries, water splitting and integrated energy systems. This article provides a timely focused review on the development of heteroatom-doped graphene materials for low-cost, but efficient, energy generation and storage.     

Rational design of MnS nanoparticles anchored on N,S-codoped carbon matrix as anode for lithium-ion batteries

The manganese sulfide (MnS) has attracted more attention as anode material on energy storage and conversion field, owing to its high theoretical capacity (616 ​mA ​h ​g⁻¹) and good electrochemical activity. However, low electronic conductivity and large volume expansion during charge-discharge processes have limited its further application. In order to address above mentioned problems, the composites, MnS nanoparticles embedded in N,S-codoped porous carbon skeleton (named as MnS/N,S–C composites), herein have been prepared successfully using metal organic framework (Mn-NTA) as template. The porous carbon skeleton not only can enhance electrode conductivity, but also relieve volume expansion during charge-discharge processes. Thus, the rational design towards electrode architectures has endowed MnS/N,S–C nanocomposites with superior electrochemical performance, which delivers the specific capacities of 676.7 ​mA ​h ​g⁻¹ at the current density of 100 ​mA ​g⁻¹.     

高性能锂离子电池负极材料一氧化锰/石墨烯复合材料的合成

通过冻干-煅烧合成了一氧化锰/石墨烯(MnO/rGO)复合材料,并将其用作锂离子电池负极材料.在500 mA·g-1的电流密度下,MnO/rGO复合材料表现出高达830 mAh·g-1的可逆容量,且在充放电循环160圈后,其可逆容量依然高达805 mAh·g-1.倍率测试结果显示,循环225圈后,在2.0 A·g-1的电流密度下,其可逆容量高达412 mAh·g-1.复合材料中的石墨烯在提高材料导电性的同时有效地缓解了一氧化锰充放电过程中的体积膨胀.通过对比容量-电压的微分分析,发现复合材料超出一氧化锰理论容量的部分是由形成了更高价态的锰引起的.MnO/rGO复合材料比纯一氧化锰(p-MnO)更容易出现高价态的锰,可能是因为rGO上残留的氧为电极反应提供了额外所需的氧源.该一氧化锰/石墨烯复合材料因其简单绿色的合成过程及优异的电化学性质,有望在未来的锂电负极中得到广泛的实际应用.     

A designed core-shell structural composite of lithium terephthalate coating on Li4Ti5O12 as anode for lithium ion batteries

A core-shell structural composite was synthesized with lithium terephthalate（Li₂C₈H₄O₄） coated on spinel Li₄Ti₅O₁₂（LTO）. The composite displays a capacity of about 200 mA h g^-1 and a good rate capability with two charge/discharge platforms at 1.55 and 0.8 V. The excellent cycling performance of the composite is attributed to the successful combination of high cycling stability of LTO and high specific capacity of Li₂C₈H₄O₄. In addition, an interesting phenomena is observed for the first time for this composite which is that lithium ions transfer between LTO and Li₂C₈H₄O₄ at a fast speed. This is investigated in details via the asymmetric charge/discharge measurement and cyclic voltammogram（CV）.The LTO/Li₂C₈H₄O₄ composite may have potential applications to be used as an anode material for the electric vehicle batteries, which is shallowly charged/discharged at ordinary times using the charge/discharge platform of LTO and fully charged/discharged at emergency to release the extra high capacity from Li₂C₈H₄O₄.     

Improving the rate capability of a SiO_x/graphite anode by adding LiNO_3

SiO_x/graphite anodes have attracted considerable attention in recent years due to their high specific capacity.Unfortunately,a thick solid-electrolyte-interface,which is produced by the decomposition of carbonate-based electrolytes,impedes the diffusion of lithium ions and significantly limits the rate performance of this interesting anode for practical applications.In this work,a LiNO_3additive was introduced during the preparation of an anode electrode paste.The results of SEM,ex and in situ XRD and XPS showed that LiNO_3decomposed into LiN_xO_yand Li_3N,which deposited on the anode surface during the first discharge process.Due to the high ionic conductivity of LiN_xO_yand Li_3N,the rate performance of the SiO_x/graphite anode was significantly improved,showing a specific capacity nearly three times higher than that without the additive.In addition,the decomposition of the electrolyte during cycling was also suppressed by the LiN_xO_yand Li_3N inorganic salts because of their low electronic conductivity and superior robustness.Our approach is facile and easy to scale up,which will be of great significance for the commercialization of SiO_x/graphite anodes.