锂/硅电池抑制硅基电极体积膨胀的方法

硅元素的含量在地壳中位列第二,而且硅基电极材料的理论比容量(4200 mAh/g)高于石墨电极(372 mAh/g)的11倍,因而成为大容量锂离子动力电池最有发展前景的电极材料之一。然而,硅基电极材料在充电过程中会产生大的体积膨胀,在放电过程中又会使电极发生体积收缩,容易导致电极材料粉化或脱落,最终使电池的循环寿命缩短,阻碍了其进一步推广和应用。针对上述问题,阐述了近年来电极材料改性、黏结剂和电解液的优化抑制硅基电极材料体积膨胀的方法进展,为大容量锂/硅动力电池的研发提供借鉴。

石墨烯的制备及其在锂离子二次电池中的应用研究进展

石墨烯是一种独特的二维纳米材料,具有许多特殊的物理化学性质,吸引了众多领域研究者的关注,已成为当今的研究热点之一。介绍了到目前为止石墨烯的主要制备方法及其优缺点,综述了石墨烯在磷酸亚铁锂电池、锂/硫电池、锂/硅电池中的应用,对石墨烯的未来发展前景做了展望。

石墨烯在锂离子二次电池中的应用进展

石墨烯是一种独特的二维纳米材料,因具有优异的物理化学性能,一经发现便引起了科研人员的重点关注,成为当今的研究热点之一。本文介绍了石墨烯的结构和主要性能,重点综述了石墨烯在磷酸亚铁锂电池、锂/硫电池、锂/硅电池中的应用,并对石墨烯的未来发展前景做了展望。

Porous silicon/carbon composites as anodes for high-performance lithium-ion batteries

Silicon anodes are promising for use in lithium-ion batteries.However,their practical application is severely limited by their large volume expansion leading to irreversible material fracture and electrical disconnects.This study proposes a new top-down strategy for preparing microsize porous silicon and introduces polyacrylonitrile(PAN)for a nitrogen-doped carbon coating,which is designed to maintain the internal pore volume and lower the expansion of the anode during lithiation and delithiation.We then explore the effect of temperature on the evolution of the structure of PAN and the electrochemical behavior of the composite electrode.After treatment at 400℃,the PAN coating retains a high nitrogen content of 11.35 at%,confirming the presence of C—N and C—O bonds that improve the ionic-electronic transport properties.This treatment not only results in a more intact carbon layer structure,but also introduces carbon defects,and produces a material that has remarkable stable cycling even at high rates.When cycled at 4 A g^(-1),the anode had a specific capacity of 857.6 mAh g^(-1) even after 200 cycles,demonstrating great potential for high-capacity energy storage applications.

A review of the carbon coating of the silicon anode in highperformance lithium-ion batteries

In the development of rechargeable lithium ion batteries(LIBs),silicon anodes have attracted much attention because of their extremely high theoretical capacity,relatively low Li-insertion voltage and the availability of silicon resources.However,their large volume expansion and fragile solid electrolyte interface(SEI)film hinder their commercial application.To solve these problems,Si has been combined with various carbon materials to increase their structural stability and improve their interface properties.The use of different carbon materials,such as amorphous carbon and graphite,as three-dimensional(3D)protective anode coatings that help buffer mechanical strain and isolate the electrolyte is detailed,and novel methods for applying the coatings are outlined.However,carbon materials used as a protective layer still have some disadvantages,necessitating their modification.Recent developments have focused on modifying the protective carbon shells,and substitutes for the carbon have been suggested.

Silane coupling agent treated copper foil as a current collector for silicon anode

Since the volume variation of silicon particles during cycling,the binding spots between Cu current collector and silicon anode raised to be one of the critical binding problems.In this work,an amino-modified Cu current collector(Cu^(*))is fabricated to tackle this issue.The amino groups on Cu^(*)surface increase its hydrophilicity,which is conducive to the curing process of aqueous slurry on its surface.Meanwhile,these amino groups can form abundant amide bonds with carboxyl groups from the adopted polyacrylic acid(PAA)binder.The combined action composed of the covalent bond and mechanical interlocking could reduce the contact loss inside the electrode.However,high concentration silane coupling agent treatment will weaken the surface roughness of Cu^(*)and weaken mechanical interlocking.What is more,the insulation of silane coupling agent reduces the conductivity of Cu and increases the impedance of battery.Considering the effect of silane coupling agent comprehensively,electrochemical performance of Cu^(*)-0.05%is best.

Synthesis and electrochemical properties of Li2FeSiO4/C/Ag composite as a cathode material for Li-ion battery

Li2FeSiO4 is deemed to be a potential candidate for large-scale applications because of its abundance,low cost and high safety,etc.Unfortunately,its low conductivity,resulting in poor rate performance,has become a main obstacle to its applications in power battery and energy storage system.In this work,C-Ag coated Li2FeSiO4 is introduced to improve the innate electronic conductivity and Li-ion diffusion ability.The results demonstrate that Li2FeSiO4/C/Ag composite exhibits better electrochemical performance.It possesses a specific discharge capacity of 152,121,108 mA.h/g at 0.2C,5C and 10C,respectively.At the same time,the Li2FeSiO4/C/Ag composite shows good cycle stability and a capacity retention ratio of 97.9%after 100 cycles at 1C.

Recycling waste crystalline-silicon solar cells: Application as high performance Si-based anode materials for lithium-ion batteries

Recycling useful materials such as Ag, Al, Sn, Cu and Si from waste silicon solar cell chips is a sustainable project to slow down the ever-growing amount of waste crystalline-silicon photovoltaic panels. However, the recovery cost of the above-mentioned materials from silicon chips via acid-alkaline treatments outweights the gain economically.Herein, we propose a new proof-of-concept to fabricate Si-based anodes with waste silicon chips as raw materials.Nanoparticles from waste silicon chips were prepared with the high-energy ball milling followed by introducing carbon nanotubes and N-doped carbon into the nanoparticles, which amplifies the electrochemical properties. It is explored that Al and Ag elements influenced electrochemical performance respectively. The results showed that the Al metal in the composite possesses an adverse impact on the electrochemical performance. After removing Al, the composite was confirmed to possess a pronounced durable cycling property due to the presence of Ag, resulting in significantly more superior property than the composite having both Al and Ag removed.

Hybrid Silicon-Carbon Nanostructured Composites as Superior Anodes for Lithium Ion Batteries

We have successfully fabricated a hybrid silicon-carbon nanostructured composite with large area （about 25.5 in^2） in a simple fashion using a conventional sputtering system. When used as the anode in lithium ion batteries, the uniformly deposited amorphous silicon （a-Si） works as the active material to store electrical energy, and the pre-coated carbon nanofibers （CNFs） serve as both the electron conducting pathway and a strain/stress relaxation layer for the sputtered a-Si layers during the intercalation process of lithium ions. As a result, the as-fabricated lithium ion batteries, with deposited a-Si thicknesses of 200 nm or 300 nm, not only exhibit a high specific capacity of 〉2000 mA.h/g, but also show a good capacity retention of over 80% and Coulombic efficiency of 〉98% after a large number of charge/discharge experiments. Our approach offers an efficient and scalable method to obtain silicon-carbon nanostructured composites for application in lithium ion batteries.

Hydrothermal synthesis of nano-silicon from a silica sol and its use in lithium ion batteries

There have been few reports concerning the hydrothermal synthesis of silicon anode materials. In this manuscript, starting from the very cheap silica sol, we hydrothermally prepared porous silicon nanospheres in an autoclave at 180 ℃. As anode materials for lithium-ion batteries （LIBs）, the as-prepared nano-silicon anode without any carbon coating delivers a high reversible specific capacity of 2,650 mAh·g^-1 at 0.36 A·g^-1 and a significant cycling stability of about 950 mAh·g^-1 at 3.6 A·g^-1 during 500 cycles.

Metal-assisted chemical etching of silicon and the behavior of nanoscale silicon materials as Li-ion battery anodes

This review outlines the developments and recent progress in metal-assisted chemical etching of silicon, summarizing a variety of fundamental and innovative processes and etching methods that form a wide range of nanoscale silicon structures. The use of silicon as an anode for Li-ion batteries is also reviewed, where factors such as film thickness, doping, alloying, and their response to reversible lithiation processes are summarized and discussed with respect to battery cell performance. Recent advances in improving the performance of silicon-based anodes in Li-ion batteries are also discussed. The use of a variety of nanostructured silicon structures formed by many different methods as Li-ion battery anodes is outlined, focusing in particular on the influence of mass loading, core-shell structure, conductive additives, and other parameters. The influence of porosity, dopant type, and doping level on the electrochemical response and cell performance of the silicon anodes are detailed based on recent findings. Perspectives on the future of silicon and related materials, and their compositional and structural modifications for energy storage via several electrochemical mechanisms, are also provided.

Silicon-based nanosheets synthesized by a topochemical reaction for use as anodes for lithium ion batteries

Silicon is the most promising anode material for the next generation high- performance lithium ion batteries. However, its commercial application is hindered by its poor performance due to the huge volume change during cycling. Although two-dimensional silicon-based materials show significantly improved performance, flexible synthesis of such materials is still a challenge. In this work, silicon-based nanosheets with a multilayer structure are synthesized for the first time by a topochemical reaction. The morphology and oxidation state of these nanosheets can be controlled by appropriate choice of reaction media and oxidants. Benefiting from the hierarchical structure and ultrathin size, when the silicon-based nanosheets are employed as anodes they exhibit a charge （delithiation） capacity of 800 mAh/g after 50 cycles with a maximum coulombic efficiency of 99.4% and good rate performance （647 mAh/g at 1 A/g）. This work demonstrates a novel method for preparing nanosheets not only for lithium ion batteries but also having various potential applications in other fields, such as catalysts, electronics and photonics.

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.