高容量型锂离子电池硅基负极材料的研究进展

硅基负极材料由于其具有高容量而被广泛研究,该材料在充/放电过程中巨大的体积变化、低的循环寿命和初始库仑效率阻碍了其商业化应用. 本文分析了硅基负极材料的工作原理,回顾了其在脱/嵌锂过程中的晶体结构、表面/界面的变化以及提高其电化学性能的方法,讨论了锂离子电池硅基负极材料的前景.     

Progress on Sn-based thin-film anode materials for lithium-ion batteries

Thin-film lithium-ion batteries are the most competitive power sources for various kinds of micro-electro-mechanical systems and have been extensively researched.The present paper reviews the recent progress on Sn-based thin-film anode materials,with particular emphasis on the preparation and performances of pure Sn,Sn-based alloy,and Sn-based oxide thin films.From this survey,several conclusions can be drawn concerning the properties of Sn-based thin-film anodes.Pure Sn thin films deliver high reversible capacity but very poor cyclability due to the huge volume changes that accompany lithium insertion/extraction.The cycle performance of Sn-based intermetallic thin films can be enhanced at the expense of their capacities by alloying with inactive transition metals.In contrast to anodes in which Sn is alloyed with inactive transition metals,Sn-based nanocomposite films deliver high capacity with enhanced cycle performance through the incorporation of active elements.In comparison with pure Sn anodes,Sn-based oxide thin films show greatly enhanced cyclability due to the in situ formation of Sn nanodispersoids in an Li2O matrix,although there is quite a large initial irreversible capacity loss.For all of these anodes,substantial improvements have been achieved by micro-nanostructure tuning of the active materials.Based on the progress that has already been made on the relationship between the properties and microstructures of Sn-based thin-film anodes,it is believed that manipulating the multi-phase and multi-scale structures offers an important means of further improving the capacity and cyclability of Sn-based alloy thin-film anodes.     

锂离子电池硅/碳负极材料的制备与应用

对锂离子电池中硅/碳负极材料的纳米结构、掺杂改性以及三元复合等制备工艺及其电化学性能、相关机理进行了总结。通过研究不同改性方法对硅/碳负极材料电化学性能的影响,以找到较为优异的改性路径。经过对比发现,通过采用纳米结构、原子掺杂以及三元复合的方法均可显著提升硅/碳负极材料的电化学性能。最后对硅/碳负极材料发展现状进行了简要分析,并对其研究前景进行了展望。     

Influence of structure and atom sites on Sn-based anode materials for lithium ion batteries: a first-principle study

To understand the influence of structure and atom sites on the electrochemical properties of Sn-based anode materials,the lithium intercalation–deintercalation mechanisms into SnNi2Cu and SnNiCu2phases were studied using the first-principle plane wave pseudo-potential method.Calculation results showed that both SnNi2Cu and SnNiCu2were unsuitable anode materials for lithium ion batteries.The Sn-based anode structure related to the number of interstitial sites,theoretical specific capacity,and volume expansion ratio.Different atom sites led to different forces at interstitial sites,resulting in variations in formation energy,density of states,and hybrid orbital types.In order to validate the calculated model,the SnNi2Cu alloy anode material was synthesized through a chemical reduction-codeposition approach.Experimental results proved that the theoretical design was reasonable.Consequently,when selecting Snbased alloy anodes,attention should be paid to maximizing the number of interstitial sites and distributing atoms reasonably to minimize forces at these sites and facilitate the intercalation and deintercalation of lithium ion.     

锂离子电池纳米负极材料的研究和开发

综述了纳米材料在负极材料方面的最新研究和开发进展,主要包括纳米金属及纳米合金、纳米氧化物、碳纳米管、具有纳米孔结构的无定形炭材料和天然石墨．由于纳米材料的特有性能,它们的可逆容量均高于目前商品化的负极材料．纳米合金负极材料的实业化存在问题,特别是循环稳定性．碳纳米管则由于制备和纯化,成本过高,规模化生产不容易实施,同时理论方面也有待于进一步的研究,以期提高其电化学性能．具有纳米孔的无定形炭材料的制备温度低,而且容量也比较高,但是对于产业化而言,循环性能和电压滞后现象有待于改进．具有纳米孔的天然石墨负极材料不仅容量高、制备比较简单、成本低,而且具有良好的循环性能,可望达到产业化的要求．     

锂离子电池二氧化锡负极材料研究进展

由于以碳为负极材料的锂离子电池(LIBs)已很难满足高性能电子产品对高能量密度的需求,因此研究新的锂离子电池负极材料成为近年来主要的研究方向。在金属氧化物中,二氧化锡(SnO_2)以其较高的理论比容量(782 mAh/g)引起了广泛的关注。首先概述了SnO_2的不同形貌如纳米颗粒、纳米棒、纳米片、纳米微球等在锂离子电池方面的特性;然后阐述了通过掺杂或修饰改善其结构及电化学性能;最后展望了SnO_2基负极材料的纳米结构设计与改进在锂离子电池领域面临的挑战。     

SrF2颗粒涂覆增强Si/C负极电化学性能

The silicon-based material exhibits a high theoretical specific capacity and is one of the best anode for the next generation of advanced lithium-ion batteries (LIBs). However, it is difficult for the silicon-based anode to form a stable solid-state interphase (SEI) during Li alloy/de-alloy process due to the large volume change (up to 300%) between silicon and Li_4.4Si, which seriously limits the cycle life of the LIBs. Herein, we use strontium fluoride (SrF₂) particle to coat the silicon?carbon (Si/C) electrode (SrF₂@Si/C) to help forming a stable and high mechanical strength SEI by spontaneously embedding the SrF₂ particle into SEI. Meanwhile the formed SEI can inhibit the volume expansion of the silicon?carbon anode during the cycle. The electrochemical test results show that the cycle performance and the ionic conductivity of the SrF₂@Si/C anode has been significantly improved. The X-ray photoelectron spectroscopy (XPS) analysis reveals that there are fewer electrolyte decomposition products formed on the surface of the SrF₂@Si/C anode. This study provides a facile approach to overcome the problems of Si/C electrode during the electrochemical cycling, which will be beneficial to the industrial application of silicon-based anode materials.     

Review of silicon-based alloys for lithium-ion battery anodes

Silicon (Si) is widely considered to be the most attractive candidate anode material for use in next-generation high-energy-density lithium (Li)-ion batteries (LIBs) because it has a high theoretical gravimetric Li storage capacity, relatively low lithiation voltage, and abund-ant resources. Consequently, massive efforts have been exerted to improve its electrochemical performance. While some progress in this field has been achieved, a number of severe challenges, such as the element’s large volume change during cycling, low intrinsic electronic conduct-ivity, and poor rate capacity, have yet to be solved. Methods to solve these problems have been attempted via the development of nanosized Si materials. Unfortunately, reviews summarizing the work on Si-based alloys are scarce. Herein, the recent progress related to Si-based alloy an-ode materials is reviewed. The problems associated with Si anodes and the corresponding strategies used to address these problems are first de-scribed. Then, the available Si-based alloys are divided into Si/Li-active and inactive systems, and the characteristics of these systems are dis-cussed. Other special systems are also introduced. Finally, perspectives and future outlooks are provided to enable the wider application of Si-alloy anodes to commercial LIBs.     

Inorganic-Organic Composite Materials for Lithium Batteries

1 Results In order to develop high capacity anode materials for enhancing the performance of lithium-ion batteries,silicon (Si) and a variety of metals that alloy with lithium,such as Sn,Sb,and Al,were studied and found to be promising candidates as anode materials[1-4].Among them,Si appears to be the most attractive candidate due to its large theoretical lithium insertion capacity of 4 200 mAh g-1[1].Unfortunately,there is one severe problem with the application of Si anode,i.e., the large volume chang...     

Sn/C复合材料的制备及作为锂离子电池负极材料的性能

采用SnCl2.2H2O乙醇溶液浸渍竹炭和NaBH4还原方法制备出一种锂二次电池负极用Sn/C复合材料。考察了复合材料中Sn含量对产物收率、微观结构及电化学性能的影响。结果表明,Sn2+大部分进入到竹炭的孔道中,并被还原为单质Sn;当单质Sn与复合材料质量比为42.5∶100时,复合电极材料具有555.1mAh/g的可逆容量,循环20次后容量保持在423.8 mAh/g,显示出较好的实用性能。     

Fe2O3在锂离子电池负极材料中的研究进展

近年来,锂离子电池被广泛地应用于便携式电子设备和手机,并且对于诸如电动汽车等更高要求的应用而言具有巨大的潜力。作为锂离子电池负极材料,Fe₂O₃是最有可能替代石墨的过渡金属氧化物之一。因其具有高的理论比容量（1 007 mA·h·g^-1）、储量丰富、安全性能好、无毒、环境友好和成本低等一系列优点,被广泛应用于气体传感器、催化和锂离子电池电极材料等领域,是一种具有巨大潜力的电极材料。介绍了锂离子电池的基本结构组成和工作原理,综述了Fe₂O₃的储锂机制和制备方法,总结了近年来Fe₂O₃以及它的复合物作为锂离子电池负极材料的研究进展。     

Low temperature synthesis of NiO/Co3O4 composite nanosheets as high performance Li-ion battery anode materials

NiO/Co3O4 composite nanosheets have been synthesized via a facile method at low temperature for the first time.The as prepared materials were characterized by X-ray powder diffraction(XRD) and transmission electron microscopy(TEM),and the performance of Li-ion batteries(LIBs) as anode materials were also studied.By controlling the atom ratio of Ni:Co,not only the size of the nanosheets can be controlled,the electrode’s conductivity and stability could also be greatly improved.The composite material showed a stable capacity retention during cycling(87% of the second capacity was retained after 15 cycles) even at a relatively large current rate(400 mA/g).The NiO/Co3O4 nanosheet might be promising candidate anode materials in high performance Li-ion batteries.     

纳米SnO2的制备及电化学性质

以无机盐为前体,采用溶胶-凝胶法制备了纳米SnO₂粉体.用TG-DTA,XRD,SEM等对SnO₂粉末进行了表征.结果表明,采用该法经500 ℃热处理得到的SnO₂超细粉具有良好的四方结构,粒径分布均匀,平均粒径在92 nm左右.将该法制得的SnO2超细粉作为锂离子电池负极材料,可逆容量高达687　mAh·g^-1,而且嵌脱锂电压低(0.2～0.5 V),是一种很有潜力的锂离子电池负极材料.     

富镍三元层状过渡金属氧化物正极材料的改性方法研究综述

富镍三元层状过渡金属氧化物正极材料因具有比容量高、价格低廉以及对环境友好等特性而备受关注,但受锂镍混排、相变反应、产气、微裂纹、过渡金属溶出、表面结构等影响,材料本身存在循环容量衰减等问题。针对正极材料循环容量衰减过快、高温性能不佳等问题,总结了近年来国内外关于富镍三元层状过渡金属氧化物正极材料的改性方法,包括表面包覆材料合成、元素掺杂材料制备、核壳结构材料开发、浓度梯度材料设计等优化方法,指出高镍层状过渡金属氧化物正极材料的应用需要从不断完善材料制备方法、改变材料性状、降低材料成本等方面入手,开发高能量密度的锂离子电池,使富镍三元层状过渡金属氧化物正极材料在动力电池领域尽早得到广泛应用。     

锂离子二次电池铜锡合金负极研究进展

与碳负极材料相比,锡基合金材料具有高容量、高密度的优势,有望成为新一代高容量锂离子电池的首选负极材料。Cu-Sn合金是研究最为广泛的锡基合金材料之一。综述了近年来该领域的研究进展,并对其发展方向进行了展望。     

A black phosphorus-graphite hybrid as a Li-ion regulator enabling stable lithium deposition

Lithium (Li) metal anodes have been regarded as the most promising candidates for high energy density secondary lithium batteries due to their high specific capacity and low redox potential. However, the issues of Li dendrites caused by nonuniform lithium deposition during battery cycling severely hinder the practical applications of Li metal anodes. Herein, a hybrid of black phosphorus-graphite (BP-G) is introduced to serve as an artificial protective layer for the Li metal anode. The two-dimensional few-layer BP, which is lithophilic, combined with the high electronic conductive graphite can act as a regulator to adjust the migration of Li ions, delivering a uniform and stable lithium deposition. As the growth of lithium dendrites is inhibited, the utilization of Li metal achieves > 98.5% for over 500 cycles in Li||Cu half cells, and the life span is maintained over 2000 h in Li||Li symmetric cells with a low voltage hysteresis of 50 mV. Moreover, the LiFePO₄||Li full cell with a BP-G Li-ion regulator presents significantly better specific capacity and cycling stability than that with the bare Li metal anode. Therefore, the introduction of the BP-G Li-ion regulator is demonstrated to be an effective approach to enable stable lithium deposition for rechargeable Li metal batteries.     

A facile method to synthesize 3D structured Sn anode material with excellent electrochemical performance for lithium-ion batteries

Sn anode materials with high specific capacity are an appealing alternative to graphite for next-generation advanced lithium-ion batteries. However, poor electrochemical performance originating from fracture and pulverization due to the enormous volume changes during lithium alloying/dealloying hinders their commercial applications. Here, we propose the synthesis of a novel 3D structured Sn anode material by a facile method: heat treatment of nanosized SnO₂ spheres in a tube furnace w...     

Application prospects of high-voltage cathode materials in all-solid-state lithium-ion batteries

All-solid-state lithium-ion batteries are lithiumion batteries with solid-state electrolytes instead of liquid electrolytes.They are hopeful in solving the safety problems of lithium-ion batteries,once their large capacity and long life are achieved,they will have broad application prospects in the field of electric vehicles and large-scale energy storage.The working potential window of solid electrolytes is wider than that of liquid electrolytes,so high-voltage cathode materials could be used in all-solidstate lithium-ion batteries to get higher energy density and larger capacity by elevating the working voltage of the batteries.The spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithium-rich cathode materials can be expected to be applied to all-solid-state lithium-ion batteries as cathode materials due to their highvoltage platforms.In this review,the electrochemical properties and structures of spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithiumrich cathode materials are introduced.More attentions are paid on recent research progress of conductivity and interface stability of these materials,in order to improve their compatibility with solid electrolytes as cathode materials in all-solid-state lithium-ion batteries and fully improve the properties of all-solid-state batteries.Finally,the existing problems of their application in all-solid-state lithium-ion batteries are summarized,the main research directions are put forward and their application prospects in all-solid-state lithium-ion batteries are discussed.     

铝电池的开发与应用进展

金属铝是一种很高的能量载体,是开发电池的理想电极材料·铝一直没有成功地应用于电化学能量储存和转换技术,是由于金属铝表面有一层保护膜,导致电极电位显著低于理论值且电压行为明显滞后,而在活化状态下铝的抗腐蚀性下降·这些问题限制了铝电池的早期开发应用·近年来通过开发各种新型的铝电极及相应电解质的添加剂,铝电池的研究取得了突破性的进展,开拓了铝的应用电化学的新领域·综合评述了近年来铝在电化学能源技术方面的研究和应用的新进展·内容按电解质体系分为水溶液电解质电池、铝空气电池和熔盐及常温有机熔盐电解质电池等·     

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.