Self-supported multi-walled carbon nanotube-embedded silicon nanoparticle films for anodes of Li-ion batteries

Self-supported multi-walled carbon nanotube (MWCNT)-embedded Si nanoparticle (NP) film electrodes for Li-ion rechargeable batteries have been prepared through chemical vapor deposition using acetylene gas and a facile spin coating process using commercial Si nanopowders. The void spaces between the MWCNTs were densely filled with a considerable amount of Si NPs with diameters of ∼50 nm. The MWCNT-embedded Si NP film electrodes showed improved cycling performance. These high electrochemical performances were ascribed to the roles of MWCNTs providing an efficient electron-transport path and alleviating severe volume change of Si NPs occurring during Li-alloying/de-alloying process.     

Reassembled graphene-platelets encapsulated silicon nanoparticles for Li-ion battery anodes

Among lithium alloy metals, silicon is an attractive candidate to replace commercial graphite anode because silicon possesses about ten times higher theoretical energy density than graphite. However, electrically nonconducting silicon undergoes a large volume changes during lithiation/delithiation reactions, which causes fast loss of storage capacity upon cycling due to electrode pulverization. To alleviate these problems, electrodes comprising Si nanoparticles (20 nm) and graphene platelets, denoted as SiGP-1 (Si = 35.5 wt%) and SiGP-2 (Si = 57.6 wt%), have been prepared with low cost materials and using easily scalable solution-dispersion methods. X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM) analyses indicated that Si nanoparticles were highly dispersed and encapsulated between graphene sheets that stacked into platelets in which portions of graphite phases were reconstituted. From the galvanostatic cycling test, SiGP-1 exhibited a reversible lithiation capacity of approximately 802 mAh/g with excellent capacity retention up to 30 cycles at 100 mA/g. Further cycling with a step-increase of current density (100-1,000 mA/g) up to 120 cycles revealed that it has an appreciable power capability as well, showing 520 mAh/g at 1,000 mA/g with capacity loss of 0.2-0.3% per cycle. The improved electrochemical performance is attributed to the robust electrical integrity provided by flexible graphene sheets that encapsulated dispersed Si nanopraticles and stacked into platelets with portions of reconstituted graphite phases in their structure.     

Three-dimensional spongy nanographene-functionalized silicon anodes for lithium ion batteries with superior cycling stability

An innovative spongy nanographene (SG) shell for a silicon substrate was prepared by low-temperature chemical vapor deposition on a hierarchical nickel nanotemplate. The SG-functionalized silicon (Si@SG) composite shows outstanding properties, which may be helpful to overcome issues affecting current silicon anodes used in lithium ion batteries such as poor conductivity, large volume expansion and high mass transfer resistance. The hierarchical nanographene shell exhibits elastic, sponge-like features that allow it to self-adaptively change its volume to accommodate the volume expansion of silicon. In addition, the porous, spongy framework containing randomly stacked graphene nanosheets presents low diffusion barriers and provides sufficiently free and short-haul channel segments to allow the fast migration of Li and electrolyte ions. The unique properties of the present silicon anode result in excellent electrochemical performances in terms of long-term cycling stability (95% capacity retention after 510 cycles), rate performance, and cycling behavior for high mass loadings at different current densities.

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Surface morphology,elastic modulus and hardness of thin film cathodes for Li-ion rechargeable batteries

In this study, surface morphology, elastic modulus and hardness of two thin film cathode materials, namely layered structured LiNi_1/3Co_1/3Mn_1/3O₂ and spinel structured LiMn₂O₄, during the charge/discharge cycles, are measured by using Scanning Electron Microscopy, Atomic Force Microscopy and nanoindentation experiments. Furthermore, the effects of depth of discharge (DOD) and charging rate (current density) on the changes of elastic modulus and hardness of the spinel structured LiMn₂O₄ are also investigated. The results have shown that both elastic modulus and hardness of the thin film cathodes have been significantly affected by the charge/discharge cycles as well as the condition of the charge/discharge processes. These results suggest the importance of the mechanical properties of the cathode materials to the reliability and integrity of the cathode materials to be used for the Li-ion batteries. The possible mechanisms of the changes in mechanical properties are also discussed.     

Fluidized bed chemical vapor deposition of silicon on carbon nanotubes for Li-ion batteries

Silicon was deposited on balls of entangled multi-walled carbon nanotubes (CNT) with a mean diameter of several hundreds of microns, by Fluidized Bed Chemical Vapor Deposition from silane (SiH4). The weight total percentage of deposited silicon was between 30 and 70%, to test their efficacy in Li-ion battery anodes. TEM and SEM imaging revealed that silicon deposits were of the form of nanoparticles uniformly dispersed on the whole CNT surface. The diameter of these nanoparticles increases with the deposited silicon percentage from 18 to 36 nm whereas their density remains constant at 5 10(22) nanoparticles/g of CNT. This indicates a low affinity of chemical species born from silane pyrolysis with the CNT surface for nucleation. The increase of the silicon nanoparticles diameter leads to the decrease of the specific surface area and the porous volume of the balls, probably due to the filling of the pores of the CNT network by silicon. A slight increase of the mean diameter of the balls was observed for the two highest silicon percentages, certainly due to the ability of the CNT network to be deformed under the mechanical stress induced by the silicon nanoparticles growth.     

Electrochemical investigation on silicon/titanium carbide nanocomposite film anode for Li-ion batteries

A Si/TiC nanocomposite film was synthesized by a surface sol-gel method in combination with a following heat-treatment process. The electrochemical properties of the film anode for lithium ion batteries were investigated by galvanostatic charge-discharge tests, cyclic voltammetry (CV) and electrochemical impedance spectrum (EIS). Because of the homogeneous distribution of Si active particles in TiC matrix, the Si/TiC composite showed reversible lithium storage capacities of about 1000 and 1300 mAh g^− 1 at 160 and 80 mA g^− 1 even after 80 cycles, respectively. Using two-parallel diffusion path model, the reactive mechanisms of Li with Si/TiC composite film were interpreted. The chemical diffusion coefficients of the Si/TiC nanocomposite film at different electrode potentials were also discussed.     

MoO(3-x) nanowire arrays as stable and high-capacity anodes for lithium ion batteries

In this study, vertical nanowire arrays of MoO(3-x) grown on metallic substrates with diameters of ~90 nm show high-capacity retention of ~630 mAhg(-1) for up to 20 cycles at 50 mAg(-1) current density. Particularly, they exhibit a capacity retention of ~500 mAhg(-1) in the voltage window of 0.7-0.1 V, much higher than the theoretical capacity of graphite. In addition, 10 nm Si-coated MoO(3-x) nanowire arrays have shown a capacity retention of ~780 mAhg(-1), indicating that hybrid materials are the next generation materials for lithium ion batteries.     

Morphology effect on the performances of SnO2 nanorod arrays as anodes for Li-ion batteries

Ni foam suppported-SnO₂ nanorod arrays with controllable diameter were prepared via a template-free growth method, which was a convenient route for the large-scale growth of pure-phase metal oxide nanorod arrays on metal substrates. The relationship between electrochemical behavior and the shape of SnO₂ nanorod arrays has been investigated in detail. SnO₂ nanorod arrays with diameter of about 25 nm, as anode materials for Li-ion batteries revealed a capacity of 607 mAh g⁻¹ (at 0.2 C) up to 50 cycles. The superior performance of the SnO₂ nanorods can be mainly attributed to small size of nanorods which reduce volume expansion and lithium diffusion length.     

One-step spray pyrolysis synthesized CuO-carbon composite combined with carboxymethyl cellulose binder as anode for lithium-ion batteries

Copper oxide-carbon composite with hollow sphere structure has been synthesized by a one-step spray pyrolysis method and tested as anode material for lithium-ion batteries. Different analytical methods, including X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometry, thermogravimetric analysis, and systematic electrochemical tests were performed. The results demonstrate that the CuO-carbon composite in conjunction with carboxymethyl cellulose (CMC) binder has an excellent electrochemical performance, with a capacity of 577 mAh g(-1) up to 100 cycles. The usage of the water soluble binder, CMC, not only obviously improves the electrochemical performance, but also makes the electrode fabrication process much easier and more environmentally friendly.     

Comparative life cycle assessment of lithium-ion batteries with lithium metal,silicon nanowire,and graphite anodes

Clean Technologies and Environmental Policy - Lithium metal and silicon nanowires, with higher specific capacity than graphite, are the most promising alternative advanced anode materials for use...     

锂离子电池正极材料的研究进展

研究与开发新型的电池正极材料是锂离子电池研究中的一项重要内容．目前正极材料的研究主要集中于3种富锂的金属氧化物LiCoO2、LiNiO2和LiMn2O4。本文主要介绍了锂离子电池正极材料的合成方法,同时比较了几种不同电极材料的结构以及电化学性能,指出了其工作特点和存在问题,并对该领域的研究现状进行了简要的综述。本文还介绍了锂离子电池正极材料计算研究的进展。利用VASP软件包可计算形成能、相图、电压和材料的晶体结构参数及态密度等。     

Mesoporous Mn-Sn bimetallic oxide nanocubes as long cycle life anodes for Li-ion half/full cells and sulfur hosts for Li-S batteries

Mesoporous Mn-Sn bimetallic oxide (BO) nanocubes with sizes of 15–30 nm show outstanding stable and reversible capacities in lithium ion batteries (LIBs), reaching 856.8 mAh·g^–1 after 400 cycles at 500 mA·g^–1 and 506 mAh·g^–1 after 850 cycles at 1,000 mA·g^–1. The preliminary investigation of the reaction mechanism, based on X-ray diffraction measurements, indicates the occurrence of both conversion and alloying–dealloying reactions in the Mn-Sn bimetallic oxide electrode. Moreover, Mn-Sn BO//LiCoO₂ Li-ion full cells were successfully assembled for the first time, and found to deliver a relatively high energy density of 176.25 Wh·kg^–1 at 16.35 W·kg^–1 (based on the total weight of anode and cathode materials). The superior long-term stability of these materials might be attributed to their nanoscale size and unique mesoporous nanocubic structure, which provide short Li⁺ diffusion pathways and a high contact area between electrolyte and active material. In addition, the Mn-Sn BOs could be used as advanced sulfur hosts for lithium-sulfur batteries, owing to their adequate mesoporous structure and relatively strong chemisorption of lithium polysulfide. The present results thus highlight the promising potential of mesoporous Mn-Sn bimetallic oxides for application in Li-ion and Li-S batteries.

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Advances in multimetallic alloy-based anodes for alkali-ion and alkali-metal batteries

In order to meet the growing demand of portable electronic devices and electric vehicles, enhancements in battery performance metrics are required to provide higher energy/power densities and longer cycle lives, especially for anode materials. Alloying anodes, such as Group IVA elements-based materials, are attracting increasing interest as anodes for next-generation high-performance alkali-metal-ion batteries (AMIBs) owing to their extremely high specific capacities, low working voltages, and natural abundance. Nevertheless, alloying-type anodes usually display unsatisfactory cycle life due to their intrinsic violent volumetric and structural changes during the charge–discharge process, causing mechanical fracture and exacerbating side reactions. In order to overcome these challenges, efforts have been made in recent years to manufacture multimetallic anodes that can accommodate the induced strain, thus showing high Coulomb efficiency and long cycle life. Meanwhile, much work has been conducted to understand the details of structural changes and reaction mechanisms taking place by in-situ characterization methodologies. In this paper, we review the various recent developments in multimetallic anode materials for AMIBs and shed light on optimizing the anode materials. Finally, the perspectives and future challenges in achieving the practical applications of multimetallic alloy anodes in high-energy AMIB systems are proposed.     

Design of hierarchical buffer structure for silicon/carbon composite as a high-performance Li-ion batteries anode

Silicon-based materials are used as anode material for lithium-ion batteries, due to ultra-high theoretical specific capacity. However, large volume changes, continuous formation of unstable solid electrolyte interface film and low conductivity greatly restricted its large-scale development and application. In this case, a composite with hierarchical buffer structure coated Si nanoparticles (Si@RF@MP) was designed and manufactured by the surfactant template and emulsification method in this study. The resorcinol–formaldehyde resin acts as the structural buffer and the conductive layer to accommodate the volume change of silicon and provide fast channels for electron transfer and lithium-ion diffusion. The unique turbostratic structure of mesophase pitch can effectively improve the integral conductivity and the structural stability of the electrode. As a result, the Si@RF@MP composite exhibited an excellent reversible discharge capacity of 389 mA h g^?1 after 200 cycles at 200 mA g^?1, and retained a discharge capacity of 345 mA h g^?1 after 300 cycles at a high current density of 1000 mA g^?1. In addition, the Si@RF@MP composite delivered reversible capacities of about 546 mA h g^?1, 495 mA h g^?1, and 437 mA h g^?1 in current densities of 500 mA g^?1, 1000 mA g^?1, and 2000 mA g^?1, respectively, indicating good rate performance. Hence, this strategy provides a new method and idea for the further development of silicon/carbon composites and a strategy to achieve high value and green utilization of pitch.

     

新型锂电池负极复合材料硅/无定形碳/碳纳米管的制备及性能研究

通过高温裂解蔗糖混合纳米硅和碳纳米管,得到硅/无定形碳/碳纳米管复合材料.实验结果表明,复合材料的首次放电容量高达1315.4mAh/g,首次充放电效率为72.4%,经过20次充放电循环后可逆容量仍高达830.5mAh/g.具有良好弹性的碳纳米管组成的网状结构使复合材料能保持较好的形貌,而碳纳米管优良的导电性可以使更多...     

低成本二氧化硅源镁热还原制备锂离子电池多孔硅负极材料的研究进展

硅材料因其超高的理论比容量、较低的放电电压及锂离子扩散势垒,成为最有发展前景的高容量锂离子电池负极材料之一.然而,硅负极在充放电过程中会引起巨大的体积膨胀,严重影响其电化学性能.设计具有纳米尺寸和多孔结构的硅负极材料是实现高容量硅负极的有效途径.但目前大多数的制备方法通常工艺复杂、成本高、产率低,限制了其商业应用.因此...     

Nanostructured Na-ion and Li-ion anodes for battery application: A comparative overview

This paper offers a comprehensive overview on the role of nanostructures in the development of advanced anode materials for application in both lithium and sodium-ion batteries. In particular, this review highlights the differences between the two chemistries, the critical effect of nanosize on the electrode performance, as well as the routes to exploit the inherent potential of nanostructures to achieve high specific energy at the anode, enhance the rate capability, and obtain a long cycle life. Furthermore, it gives an overview of nanostructured sodium- and lithium-based anode materials, and presents a critical analysis of the advantages and issues associated with the use of nanotechnology.

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锂离子电池LiFeO2基材料研究进展

LiCoO2是目前商品锂离子电池中最广泛应用的正极材料,然而其价格昂贵且对环境有害,促使人们研究开发新型正极材料。由于Fe是地球上最丰富且无毒的金属,具有与LiCoO2相似岩盐结构的LiFeO2研究引起人们广泛关注。综述了LiFeO2基锂离子电池材料的研究进展,评述了制备与性能,展望了LiFeO2基锂离子电池材料未来的发展方向和应用前景。