石墨烯/聚苯胺复合阳极的制备及在MFC中的应用

采用化学氧化还原法制备高纯度石墨烯（GR）,利用电化学修饰法得到石墨烯/聚苯胺（GR/PANI）膜阳极,采用红外光谱（FI-IR）、X射线衍射（XRD）、场发射扫描电镜（FESEM）对所制备复合电极进行了表征,采用循环伏安法（CV）、交流阻抗法（EIS）考察了复合电极的电化学性能。将GR/PANI膜阳极应用于固定床微生物燃料电池（MFC）,考察了电池的产电性能。均匀地附着在石墨烯表面,GR/PANI膜电极具有良好可逆性,其电阻小、导电性良好。GR/PANI膜阳极应用于MFC,最大功率密度和开路电压分别为230.2 mW·m^-2和834.6 mV,比未修饰阳极的最大功率密度和开路电压分别提高了110.6%和34.8%,GR/PANI膜阳极的表观内阻也由未修饰阳极的843.2Ω降低为469.4 Ω,且电池启动时间大大缩短,产电稳定性增强。结果表明,GR/PANI复合物是一种优良的电极材料,GR/PANI膜阳极MFC具有良好的产电性能。     

A review study on the recent advances in developing the heteroatom-doped graphene and porous graphene as superior anode materials for Li-ion batteries

Graphene materials, with their distinctively fascinating physicochemical properties, have been receiving great attention as favorable anode materials for use in Li-ion batteries (LIBs). However, the high affinity of graphene nanosheets to restack and agglomerate during electrode assembly reduces the deliverable specific capacity due to the limited available surface area and active sites for Li-ion storage. Furthermore, the high aspect ratio of graphene nanosheets could result in long transport pathways for Li-ions and consequently limiting the rate performance. These drawbacks can be significantly improved via the functionalization of graphene by various heteroatoms and also the formation of porous graphene, adding unique beneficial properties to the inherent characteristics of graphene. Here, a comprehensive review of porous and/or heteroatom doped graphene anode materials for LIBs is presented, which summarizes in detail the main recent literature from their procedure, optimum synthesis parameters, relevant mechanisms, and the obtained morphology/structure to their electrochemical performance as the LIBs anode. Finally, the research gaps are proposed. This review will promote the basic understanding and further development of porous and/or doped graphene materials as anodes for LIBs.     

S-doped crosslinked porous Si/SiO2 anode materials with excellent lithium storage performance synthesized via disproportionation

The volume expansion during cycling and low electrical conductivity of a Si anode limit its commercial development. Nanostructure can effectively alleviate the volume expansion and doping can increase the electrical conductivity of silicon. Hence, in this paper, uniformly S-doped crosslinked porous Si/SiO₂ (S-doped pSi/SiO₂) were prepared by the disproportionation reaction of SiO at a high temperature. As a bifunctional additive, sulphur can be used to prepare crosslinked porous silicon by a silicon-sulphur reaction. Furthermore, sulphur can improve the conductive properties of the bulk Si via doping. At the same time, residual SiO₂ can also be used as a buffer material. This strategy not only provides space for the volume expansion of silicon, but also enhances its electrical conductivity and improves charge transfer. Consequently, the S-doped pSi/SiO₂ anode exhibits superior cycling capacity and rate performance (1035 mAh·g^?1 at 1 A g^?1 after 300 cycles and an exceptional rate performance of 1233 mAh·g^?1 at 2 A g^?1). Moreover, the electrochemical performance of the S-doped pSi/SiO₂//LiFePO₄ full cell was also evaluated, which exhibits favourable lithium storage performance.     

结构有序的Si/void/C/graphene纳米复合结构的制备及储锂性能

采用简单的超声、冷冻干燥和热还原相结合的自组装方法,设计和构建了纳米硅核/间隙/无定形碳壳层/石墨烯（Si/void/C/graphene） 三维有序纳米复合结构。在该结构中,纳米硅核与碳壳层之间的空隙有效避免了硅的巨大体积膨胀对碳层的破坏,大幅度提高了锂离子电池的循环稳定性;将Si/void/C纳米结构嵌入在石墨烯层与层之间,利用石墨烯卓越的导电性和柔韧性,进一步缓冲了硅材料的体积效应和提高了复合材料的导电性能。该复合材料在4200 mA·h·g^-1（1 C）电流密度下循环1000次后比容量仍高达1603 mA·h·g^-1;在67 A·g^-1（16 C）的高倍率下,比容量仍有310 mA·h·g^-1,显示出了在锂离子电池负极材料领域的巨大应用潜力。     

One-dimensional core-shell composite of AgNWs@Si@GO for high-specific capacity and high-safety anode materials of lithium-ion batteries

Si/C composite materials used for Lithium-ion battery anode, have received widespread attention owing to theirs superior energy density, long cycle life, and low self-discharge efficiency. However, the unstable solid electrolyte interface (SEI) and severe volume expansion, occurring in lithiation-delithiation of silicon materials, are major obstacles to its commercial application. Here, we proposed a silver nanowire@silicon@graphene oxide (AgNWs@Si@GO) core-shell structure by introducing one-dimensional silver nanowire into reactive silicon material through an uncomplicated polyol method. The electrochemical properties of the prepared AgNWs@Si@GO composites were well characterized as the anode of Lithium-ion batteries (LIBs). The synthesized AgNWs@Si@GO composites exhibited exceptional electrochemical performance, high specific capacity (1384.8 mA h/g at 0.2 C) and improved cycle stability. The excellent electrical conductivity of AgNWs and the outstanding flexibility of GO makes AgNWs@Si@GO core-shell structure efficaciously alleviate the volume expansion of silicon-based materials in the process of lithiation, and further improve the cycle stability of electrode materials.     

Microwave self-assembly of 3D graphene-carbon nanotube-nickel nanostructure for high capacity anode material in lithium ion battery

We report a microwave-assisted synthesis of a self-assembled three-dimensional graphene-carbon nanotube-nickel (3D G-CNT-Ni) nanostructure, which can be used as a high capacity anode material in lithium-ion batteries (LIBs). The unique 3D G-CNT-Ni nanostructure shows that CNTs are grown on graphene sheets through tip growth mechanism by Ni nano-particles. Bunches of CNTs and graphene sheets produce 3D network nanostructures with ultrahigh surface area, a large number of activation sites, and efficient ion pathways, all of which are crucial for high capacity anode materials in LIBs. The synthesized 3D nanostructure maintains a reversible specific capacity of 648.2 mA h/g after 50 cycles at a current density of 100 mA/g, as high capacity electrode structures in LIBs.     

Preparation of graphene supported porous Si@C ternary composites and their electrochemical performance as high capacity anode materials for Li-ion batteries

Graphene supported porous Si@C ternary composites had been synthesized by various routes and their structural, morphological and electrochemical properties were investigated. Porous Si spheres coated with carbon layer and supported by graphene have been designed to form a 3D carbon conductive network. Used as anode materials for lithium ion batteries, graphene supported porous Si@C ternary composites demonstrate excellent electrochemical performance and cycling stability. The first discharge capacity is 2184.7 mA h/g at a high current density of 300 mA/g. After 50 cycles, the reversible capacity is 652.4 mA h/g at a current density of 300 mA/g and the coulomb efficiency reaches at 98.7%. Due to their excellent electrochemical properties, graphene supported porous Si@C ternary composites can be a kind of promising anode materials for lithium ion batteries.     

Densely-stacked N-doped mesoporous TiO2/carbon microsphere derived from outdated milk as high-performance electrode material for energy storages

Spherical N-doped mesoporous TiO₂/C (MTC) composite micro-particles are produced by spray drying (SD) and carbonization process. The particle size of MTC microsphere is between 2 and 3.4?µm, and the N-doped amorphous C around TiO₂ could provide a conductive matrix, and buffer the volume change. When evaluated as electrodes for Li-ion batteries (LIBs) and Li-S batteries (LSBs), the MTC microsphere exhibits relatively high discharge-voltage plateau, excellent capacity retention and rate capability. As anode for LIBs, after 200 cycles, a reversible capacity more than 230?mA?h?g^?1 can achieved at 1?C. And for LSBs, a specific capacity of 1317.7?mA?h?g^?1 at 1?C and the capacity retention of 73.8% after 500 cycles. The superior electrochemical performance is ascribed to robust scaffolding architecture and conductive N-doped carbon matrix. The excellent electrochemical performance and process ability of the MTC microspheres make them very attractive as electrode materials for use in high rate battery application.     

锰氧化物的合成及在锂离子电池中的应用进展

能源是限制人类发展的重要因素,近年来随着新能源的发展,人们对于储能设备的要求也越来越高,其中,锂离子电池被认为是最具有发展前途的储能设备之一。目前,商用锂离子电池的负极材料以石墨为主,石墨虽然具有良好的导电性,但理论容量较低,已逐渐无法满足高能设备的大容量需求。过渡金属锰氧化物由于储量丰富、氧化形态多样、结构多元、理论比容量高、环境友好等特点,被认为是锂离子电池理想的替代负极材料之一。本文详细介绍了近年来4种锰氧化物（MnO、Mn₂O₃、Mn₃O₄和MnO₂）分别在纳米化和复合结构构筑两方面的材料设计及合成,总结比较了4种锰氧化物用作锂离子电池负极材料的性能,展望了锰氧化物在锂离子电池负极材料领域的发展前景和方向。     

Vertically ordered Ni(3)Si(2)/Si nanorod arrays as anode materials for high-performance Li-ion batteries

In this paper, we have reported a novel hierarchical nanostructure made of vertically ordered Ni(3)Si(2)/Si nanorod arrays to moderate the notorious pulverization and capacity decay usually occurring in the silicon used as the anode materials in Li-ion batteries. During the lithiation and delithiation process, the amorphous Si (a-Si) layer acts as an active material and participates in the processes, whereas the Ni(3)Si(2) nanorod arrays work as a mechanically stable supporter and fast charge transport pathway. In addition, they can afford sufficient interspace for expansion/contraction upon lithium insertion/extraction. These Ni(3)Si(2)/Si nanorod arrays anodes exhibit excellent cycling performance at high current rates of 1 C (4.2 A g(-1)), 2 C (8.4 A g(-1)), and 4 C (16.8 A g(-1)), respectively. A high and steady discharge capacity of over 2184 mA h g(-1) can be achieved after 50 cycles with a high initial coulombic efficiency of 86.7%. The synthesis approach is simple, efficient and rich-yielding, probably providing a new strategy for the application of silicon-based anode materials with enhanced performance.     

Molybdenum carbide embedded in carbon nanofiber as a 3D flexible anode with superior stability and high-rate performance for Li-ion batteries

The fabrication process and material design of flexible lithium-ion batteries (LIBs) are essential in flexible portable devices. In particular, the carbon nanofiber (CNF)-based active anodes with flexibility synthesized using an electrospinning technique showed fairly stable cycling performance in the LIBs. In this study, we synthesized the molybdenum carbide (MoC) embedded in CNFs as an anode for LIBs (MoC/CNF) using an electrospinning technique with amorphous Mo precursor and polyacrylonitrile as the molybdenum and carbon sources, respectively, and using a heating process under an N₂ atmosphere. The as-prepared flexible MoC/CNF showed a 3D porous structure consisting of crystalline MoC and amorphous CNF. MoC/CNF, directly utilized as an active electrode without binder, conductor, or current collector, exhibited superior LIB performance, i.e. high capacity, cyclability, and high-rate properties. In particular, at a considerably high charge/discharge rate of 10?A?g^?1, the specific capacity of MoC/CNF (109?mAh?g^?1) was significantly higher than that of pure CNF electrode (3?mAh?g^?1).     

Nanosized Si/cellulose fiber/carbon composites as high capacity anodes for lithium-ion batteries: A galvanostatic and dilatometric study

Recently, we reported a simple method for obtaining nanosized silicon with promising electrochemical properties as an anode material for lithium-ion batteries; the method involves the formation of a composite electrode with cellulose fibers. It is demonstrated that the performance of these electrodes can be enhanced by the addition of conductive carbon black (CCB). This beneficial effect is not only a result of the improvement of electrical conductivity and inter-particle contacts, but also due to a reduction of the expansion and shrinkage undergone by the electrode when Li is inserted into Si or extracted from Li_xSi, as revealed by in situ electrochemical dilatometry measurements. The best results were obtained with a CCB of high surface area and porosity. The Si/cellulose fiber/carbon electrodes obtained delivered charge capacities as high as 1800 mAh g⁻¹ and exhibited good capacity retention on cycling. These electrodes also exhibited lower expansion/shrinkage compared to carbon-free electrodes on discharging and charging the cell, respectively.     

Carbon-coated porous Si/C composite anode materials via two-step etching/coating processes for lithium-ion batteries

A highly stable Si/SiO_x/C composite was synthesized in this study through NaOH etching and carbon-coating approaches for use as an anode material in Li-ion batteries (LIBs). The two-step process not only enhanced the electronic conductivity of the as-synthesized Si/SiO_x/C composite by using the two-step etching/coating processes to enhance the columbic efficiency of Si during cycling processes but also architecturally provided an amorphous Si/SiO_x composite to buffer volume expansion. The Raman spectroscopy and X-ray diffraction results demonstrate that the etching process involves a transition from crystalline Si to amorphous SiO_x. The Fourier transform infrared spectroscopy results further confirm that the vibration mode of Si–O bonding changes from symmetric to asymmetric. The Brunauer–Emmett–Teller analysis reveals that we can control specific surface area and pore-size distribution of NaOH-modified Si by tuning the parameters pertaining to the solid content of Si in NaOH solution. After optimizing the etching and carbon-coating processes, the modified Si/C composite delivered ~780 mAh g⁻¹ for more than 200 cycles at 0.5C, which was better than un-modified one of 315 mAh g⁻¹ after 200 cycles. The results clearly indicate that we could improve cycle stability of Si anode drastically through the NaOH etching process and carbon coating modification. The proposed methodology may provide a potential approach to promoting the synthesis of Si-based anodes for use in the commercial applications of LIBs.     

Graphenothermal reduction synthesis of MnO/RGO composite with excellent anodic behaviour in lithium ion batteries

Mn(II) oxide/graphene oxide (MnO/RGO) composites were synthesized by an easy and cost-effective graphenothermal reduction method. The surface morphology, structure, chemical composition and electrochemical behaviour of the resulting composites were investigated in detail. The MnO/RGO composite exhibited a high surface area (115.7 m²/g), which led to the high discharge capacity, enhanced cycling stability, and outstanding rate capability as anode in Li-ion batteries (LIBs). The MnO/RGO composite exhibited an higher initial discharge capacity of 1607 mA h/g at a current density of 100 mA/g and maintained 94% of its reversible capacity over 100 consecutive cycles. Furthermore, MnO/RGO composite could preserve a significantly higher capacity of 847 mA h/g for 150 cycles even at a high current density of 250 mA/g. The excellent electrochemical properties result from the existence of highly conductive RGO and a short transportation span for both Li-ions and electrons. The developed MnO/RGO composite materials hold highly promising prospects in LIBs.     

石墨烯/SnO2/Si@PPy复合材料制备及电化学性能

以氧化石墨烯和SnCl2为原料，通过微波水热法合成了石墨烯/SnO2复合材料(GS)，以过硫酸铵为引发剂，通过吡咯在Si粉表面原位氧化聚合制备了Si@PPy包覆结构(SP)，最后通过微波水热组装法制备了石墨烯/SnO2/Si@PPy复合材料(GSSP)。采用SEM、TEM、XRD、Raman和BET对GS、SP和GSSP材料的形貌和结构进行表征，并以GSSP复合材料为负极组装半电池进行倍率、循环、CV和EIS等电化学性能测试。结果表明：GSSP复合材料具有优异的倍率性能，在100 mA/g电流密度下，放电和充电的平均比容量分别为948.44和869.63 mAh/g。1000 mA/g电流密度下，经过400次循环放电和充电的比容量保持率高达90.69%和89.34%。     

Graphene/nanosized silicon composites for lithium battery anodes with improved cycling stability

Graphene/nanosized silicon composites were prepared and used for lithium battery anodes. Two types of graphene samples were used and their composites with nanosized silicon were prepared in different ways. In the first method, graphene oxide (GO) and nanosized silicon particles were homogeneously mixed in aqueous solution and then the dry samples were annealed at 500 °C to give thermally reduced GO and nanosized silicon composites. In the second method, the graphene sample was prepared by fast heat treatment of expandable graphite at 1050 °C and the graphene/nanosized silicon composites were then prepared by mechanical blending. In both cases, homogeneous composites were formed and the presence of graphene in the composites has been proved to effectively enhance the cycling stability of silicon anode in the lithium-ion batteries. The significant enhancement on cycling stability could be ascribed to the high conductivity of the graphene materials and absorption of volume changes of silicon by graphene sheets during the lithiation/delithiation process. In particular, the composites using thermally expanded graphite exhibited not only more excellent cycling performance, but also higher specific capacity of 2753 mAh/g because the graphene sheets prepared by this method have fewer structural defects than thermally reduced GO.     

A review study on titanium niobium oxide-based composite anodes for Li-ion batteries: Synthesis,structure, and performance

The growing demands for Li-ion batteries (LIBs) in the electrification revolution, require the development of advanced electrode materials. Recently, intercalating titanium niobium oxide (TNO) anode materials with the general formula of TiNb_xO_2+2.5x have received lots of attention as an alternative to graphite and Li₄Ti₅O₁₂ commercial anodes. The desirability of this family of compounds stems from their high theoretical capacities (377–402 mAh/g), high safety, high working voltage, excellent cycling stability, and significant pseudocapacitive behavior. However, the rate performance of TNO-based anodes is poor owing to their low electronic and ionic conductivities. TNO-based composites generally are prepared with two aims of enhancing the conductivity of TNO and achieving a synergic effect between the TNO and the other component of the composite. Compositing with carbon matrices, such as graphene and carbon nanotubes (CNTs) are the most studied strategy for improving the conductivity of TNO and optimizing its high-rate performance. Also, for obtaining anode materials with high capacity and high long-term stability, the composites of TNO with transition metal dichalcogenides (TMDs) materials were proposed in previous literature. In this work, a comprehensive review of the TNO-based composites as the anodes for LIBs is presented which summarizes in detail the main recent literature from their synthesis procedure, optimum synthesis parameters, and the obtained morphology/structure to their electrochemical performance as the LIBs anode. Finally, the research gaps and the future perspective are proposed.     

The structural evolution and lithiation behavior of vacuum-deposited Si film with high reversible capacity

The silicon film (6 μm) was prepared by vacuum deposition method on a surface modified copper foil as anode for lithium-ion batteries with high capacity and long cycle life. The modified copper foil has a rough and pyramid-like surface which helps the deposited Si film to connect toughly. The deposited hill-like Si is favorable to reduce the mechanical stress coming from the volume expansion and shrinkage of active materials during lithiation and de-lithiation. Moreover, the Si film exists mostly in an amorphous state. After cycling, partial amorphous phase transforms into the polycrystalline Si grains, forming a combination of amorphous and crystalline structure. Cyclic voltammograms (CVs) and electrochemical impedance spectra (EIS) research indicate that the vacuum-deposited thick Si film has a good reversibility of lithiation/de-lithiation. As a consequence, the thick Si film exhibits an excellent cycling performance with high reversible capacity.     

Performance Improvement of Graphene/Silicon Solar Cells via Inverted Pyramid Texturation Array

Silicon - Graphene/silicon (Gr/Si) solar cells have aroused extensive research interest due to their simple structure and great potential for low-cost photovoltaic applications. Enhancing light...     

Effects of surrounding confinements of Si nanoparticles on Si-based anode performance for lithium ion batteries

We report herein the effects of various surrounding confinements of Si nanoparticles on the electrochemical performance of Si nanoparticles based anode for lithium ion batteries (LIBs). Three different types of surrounding confinements are incorporated onto or around the surface of Si nanoparticles: Si nanoparticles-embedded carbon nanofibers (Si@CNF) via electrospinning, carbon nitride encapsulated Si nanoparticles with core/shell structure (Si@CND), and binder enriched Si nanoparticles-based anode (Si@RBD). Morphology and microstructure of the samples are characterized using X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, and the results were discussed in relation to the electrochemical performances. It is found that Si@CNF which has conducting hard surrounding confinements and Si@RBD exhibited high reversible specific capacity of 620 mA hg⁻¹ and 1200 mA hg⁻¹, up to 30th cycle, respectively. Meanwhile, Si@CND that has mechanically hard but poor electrical conductivity exhibits low specific capacity compared with the other two samples.