Transmission electron microscopy of lithium ion battery materials

理解材料的构-效关系是功能材料领域的永恒话题,在锂离子电池材料的研究中亦是如此。因此可以看到如X射线衍射、中子衍射、核磁共振、X射线电子能谱等结构表征手段被应用于锂离子电池材料的研究中。但是因上述方法对于微观局域结构并不敏感,而给出平均的结构信息。材料的性能往往随微观结构的不同而天差地别,因此获取锂离子电池材料的微观结构信息十分重要。透射电子显微镜具有原子尺度的空间分辨能力,可以获取原子尺度上的结构扭曲和电子结构变化,在锂离子电池材料的研究中起到了至关重要的作用。本文从电子显微学和锂离子电池材料的关系入手,从基本原理和实验方法出发,为相关领域科研人员提供便利。     

Research progress on safety of lithium ion battery electrolyte

锂离子电池的能量密度及其安全问题是限制其在电动汽车应用中的主要障碍。随着能量密度的不断提升,当务之急是有效解决锂离子电池的安全性问题。锂离子电池安全问题本质上与当前电解液中使用的高挥发性、易燃的有机溶剂有关。因此,本文主要从电解液的燃烧性角度,介绍了电解液在锂离子电池材料安全性方面的研究现状,包括阻燃添加剂、不燃性氟代有机溶剂、高浓度电解液及固液混合电解质的应用等,分析其对安全性能提升的机理,并对电解液的发展方向进行了展望。     

Patent analysis of lithium ion power battery recycling technology

锂离子动力电池的回收是当前储能产业关注的焦点之一,为了解锂离子动力电池的回收现状,以CNABS和DWPI专利数据库中的检索结果为分析样本,对锂离子动力电池回收技术的专利申请量趋势、全球分布区域、国内外主要申请人、全球重点技术分布以及国内重点技术进行全面分析,结果表明,虽然锂离子动力电池回收技术是目前全球尤其是中国争相布局的产业对象,但目前各个企业的专利申请量均较小且技术布局零散,总体来说锂离子动力电池回收技术仍处于摸索阶段,产业前景不明,本文以期给锂离子动力电池回收技术未来的布局和发展提供一定的借鉴。     

Studies on the standard of lithium ion battery separator

隔膜是保障电池安全、影响电池性能发挥的重要材料。随着隔膜产业在中国的快速发展,我国的隔膜产能已经排进了世界前列。产品系列化、产品质量标准化、检测标准规范化是我国隔膜产业做大、做强的必要环节。分析了国内涉及隔膜的相关标准情况,并主要针对隔膜的检测方法及参考的标准做解读。     

Studies on the standard of lithium ion battery electrolyte

电解液是锂离子电池关键技术之一,在正负极之间起着输送和传导电流的作用,是连接正负极材料的桥梁。它影响着电池的工作电压、能量密度和安全性能等。近年来随着正负极材料的技术进步,电解液为了实现与新材料的匹配,在组分上出现了很大变化,现有的锂电池电解液标准及相应的测试方法也需要进一步更新,才能实现产品的检验规范化和质量标准化。本文介绍了电解液的现状及发展趋势,分析了我国现有电解液相关标准的情况,并对新的电解液国标提出了建议。     

Progress on high energy density lithium batteries by CAS battery research group

提高动力电池的能量密度将显著延长续航里程,对发展电动汽车具有重要的意义.中国科学院在2013年底部署了中国科学院战略性先导科技专项,通过合作研究,积极探索了第三代锂离子电池,固态锂电池,锂-硫电池和锂-空气电池等电池体系.其中,采用纳米硅碳负极,富锂正极的24 A·h的锂离子电池单体,质量能量密度达到374 W·h/kg,体积能量密度达到577 W·h/L.8 A·h固态聚合物锂电池60 ℃下能量密度达到240 W·h/kg,基于无机陶瓷固态电解质的固态锂电池室温下能量密度达到240 W·h/kg.37 A·h的锂硫电池单体室温能量密度达到566 W·h/kg,50 ℃达到616 W·h/kg.5 A·h锂空气电池单体能量密度达到526 W·h/kg.目前这些样品电池在综合技术指标方面离实际应用还有较大的距离,需要进一步深入细致的进行基础科学与关键技术方面的研究.从长远考虑,电池能量密度的提高必然进一步增加电池安全性风险,因此不同形式的固态锂电池将是未来长续航动力锂电池的发展方向.     

Application of lithium ion phosphate battery in 110 kV substation DC power system

本项目选用了两种不同的电池管理模式对磷酸铁锂电池组进行管理,并将组装好的两套电池组应用于110 kV变电站直流系统的日常运行.运行结果表明,磷酸铁锂电池可以在变电站替代铅酸蓄电池使用,并且可以浮充运行;运行过程中,单体电池的电压会由于电池充电态的变化下降或上升;单体电池的内阻呈现先下降再上升的变化;电池组的放电容量随着运行时间的延长出现每年3%左右的衰减(浮充电压为3.6 V);合适的电池管理模式能将电池组内单体电池的电压差保持在较小的范围,有利于电池组长寿命的运行.     

Numerical simulation of lithium‐ion battery performance considering electrode microstructure

A spatially resolved three‐dimensional microscale model of a lithium‐ion battery half‐cell is developed and applied to periodic electrode microstructures made up of spherical particles following a bidisperse particle size distribution. The geometries of the periodic unit cells are derived from discrete element simulations using periodic boundary conditions. Three different particle arrangements, which consist of two layered structures and one mixed particle array, as well as three different compression rates, are considered. In the study, the cathode is assumed to consist of LiMn₂O₄ as active material. Layered particle arrangements comprising the particle fraction of the smaller particle size in the region close to the separator are found to be beneficial especially for high‐rate applications. According to the simulation results, the high‐rate capability is reduced upon compression of the electrode microstructures. Copyright © 2015 John Wiley & Sons, Ltd.     

Research progress of novel binders for silicon-based anode in lithium ion battery

硅基材料由于具有超高的理论比容量,安全的嵌锂工作电位和廉价易得等诸多优点,是下一代高比能量电池体系最理想的负极材料。尽管硅基材料的研究已经进行很长时间,但是硅基材料嵌锂时巨大的体积膨胀,循环性能较差等问题一直难以得到有效解决。开发高性能硅基负极黏结剂是解决硅基材料应用问题的重要途径之一,具有“刚柔并济”结构特性的黏结剂分子能够有效抑制硅基材料结构膨胀粉化,保持电极导电网络的完整性,从而有效提升其循环性能。本文综述了硅基负极黏结剂的特性要求,新型硅基负极黏结剂的研究进展,并对该领域未来潜在的研究方向进行了展望：复合体系聚合物黏结剂的开发;特殊空间构型黏结剂的开发;新型导电黏结剂的开发;自支撑无黏结剂硅基负极的开发。     

The capacity matchup design and its effects on the performances of LTO lithium ion battery

本研究以三元NCM为正极材料,钛酸锂LTO为负极材料制作了软包装锂离子电池,并通过固定正极容量,变化负极容量的方式设计4种不同的N/P比电池,并对不同N/P比钛酸锂电池的电池容量、高温存储和循环性能进行了研究,结果显示N/P比设计对正负极材料克容量发挥,电池容量发挥,高温存储和循环性能均具有较大影响。提高N/P比可以提高电池初始放电容量,提高正极克容量发挥。但提高N/P比会使得正极电极电位提高,特别是在接近满充电状态时,电解液易在正极侧发生氧化反应。而低的N/P比可以保证正极具有低的电极电位,从而降低在进行高温存储和循环测试时电池内部的副反应,有利于改善电池高温存储性能和循环性能。对能量密度要求不高时,为了保证长寿命循环和良好的高温性能,可以适当降低N/P比到0.85~0.9之间。     

Low temperature thermal safety performance of soft packaged lithium iron phosphate battery

本文以剩余容量接近80%的软包磷酸铁锂电池为研究对象,研究其在-10 ℃低温充放电循环后的安全性能.对低温和常温循环后的电池进行热失控实验分析,同时解剖电池并测试电池材料的锂元素含量和热稳定性能.测试结果表明,电池低温循环过程中容量急剧衰减,低温循环后电池热失控温度明显降低,低温循环过程中电池负极析出了锂单质,电池材料的热稳定性也发生了变化.另外,还对低温循环后的电池进行了满电状态下的常温搁置实验,实验过程中电池全部产生胀气现象,通过进一步测试分析发现,气体以CO和H₂为主.与新电池对比发现,剩余容量接近80%的软包磷酸铁锂电池低温下充放电循环更容易产生锂枝晶,造成其电化学性能发生严重的不可逆衰退,热失控温度明显提前,因此剩余容量接近80%的磷酸铁锂电池应避免在低温下运行.     

Research status of iron based fluoride cathode materials for lithium ion battery

随着新能源技术的不断发展,对锂离子电池的能量密度要求越来越高。氟化铁（FeF₃）和氟化亚铁（FeF₂）因具有较小的分子量、多电子转化反应及高电压等优点正成为极具发展潜力的高比能锂电正极材料,但是导电性差、转化反应使得材料需要较大过电势,这制约了其实际应用。本文首先介绍了FeF₃和FeF₂的基本性质及储锂机制,随后具体论述了两者的电化学性能改进措施,主要包括对FeF₃和FeF₂进行晶体结构扩展和元素替换而出现的很多铁基氟化物新相（氟化铁的水合物Fe_xF_y·mH₂O、氟氧化铁FeOF）,纳米多孔结构的设计,碳纳米复合材料构建的研究,并简要展望了未来的发展方向。     

Modularized battery management for large lithium ion cells

A modular electronic battery management system (BMS) is described along with important features for protecting and optimizing the performance of large lithium ion (LiIon) battery packs. Of particular interest is the use of a much improved cell equalization system that can increase or decrease individual cell voltages. Experimental results are included for a pack of six series connected 60 Ah (amp-hour) LiIon cells.     

The technical route exploration of lithium ion battery with high safety and high energy density

发展高比能动力锂离子电池是新能源汽车,特别是纯电动汽车实现长续航里程的关键手段之一,然而,随着电池能量密度的不断提高,电池的循环寿命和安全性能就会受到影响。本文以能量密度300W·h/Kg单体电池为对象,从材料体系的选择、电芯结构设计以及系统安全防护措施等多维度展开论述,探究了高安全高比能动力锂离子电池系统技术路线。     

Correlating uncertainties of a lithium‐ion battery – A Monte Carlo simulation

Safety issues raised from a lithium‐ion battery during operation can be attributed to the variation of its temperature, which is, in turn, associated with the uncertainties in the parameters such as material properties and operating conditions. In this study, a Monte Carlo simulation of a mechanistic lithium‐ion battery model is conducted to capture the probabilistic nature of uncertainties in the parameters and their relative importance to the temperature of a lithium‐ion battery cell. Sensitivity analysis is statistically performed, and the varied parameters are ranked according to their contributions to the variation of the battery temperature. Statistical analysis is also conducted on the distribution of the temperature and deviation from its normality has been identified. These analyses can provide valuable information for manufactures in the area of resource partitioning for quality and safety control. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of SnO2/C anode for lithium ion battery by a reflux-assisted hydrothermal method

以氯化亚锡(SnCl₂·2H₂O)及聚乙烯吡咯烷酮(polyvinylpyrrolidone,PVP)为原料,通过回流辅助水热法制备了SnO₂/C复合材料并将其用作锂离子电池负极材料.采用X射线衍射仪(XRD),扫描电子显微镜(SEM)和透射电子显微镜(TEM)分析材料的结构和形貌;用恒流充放电,交流阻抗(EIS)和循环伏安(CV)对复合材料作为锂离子电池负极材料的电化学性能进行表征.所制备的复合材料中,纳米SnO₂晶粒(5~10 nm)均匀分散在由PVP热解形成的无定形碳中.电化学性能测试表明,该复合材料100次循环后,可逆容量为591.7 mA·h/g,呈现较好的循环性能.优异的电化学性能主要归因于纳米SnO₂颗粒在无定形碳基体中均匀分散及无定形碳对锡颗粒体积变化的有效缓冲.     

Photovoltaic grid stabilization system using second life lithium battery

The operation of residential solar photovoltaic arrays are typically dependent on net energy metering (NEM) tariffs or feed in tariffs that allow the array owner to treat the electricity grid as an energy storage device. This study presents a model and simulation results of a photovoltaic array paired with a second life battery pack, a partially degraded lithium battery pack from an automotive application, for stabilizing the electricity grid interactions of residential photovoltaic systems and reducing the overall residential demand placed on the electricity grid. Two numerical simulations are performed on the operation of a second life battery pack. The first used an equivalent system model for the battery pack and measured solar production and residential loads to evaluate the system performance using one second time steps. The second model used hourly time steps and round trip efficiency for the battery, coupled with weather data and residential demand, to determine the system performance over the course of a year. The numerical investigation shows that the PV and battery system can substantially reduce the quantity of solar electricity that is exported to the distribution grid and decrease the impacts of sudden fluctuations in photovoltaic output due to cloud cover while providing significant reductions in the electricity demand placed on the grid. Copyright © 2015 John Wiley & Sons, Ltd.     

Technology progress of cathode materials for lithium ion batteries

本文针对商业化锂离子电池正极材料,介绍了钴酸锂、镍钴锰三元材料、尖晶石锰酸锂、磷酸铁锂等正极材料的优缺点、市场现状,以及我国正极材料的技术和产业现状。对行业存在的共性问题,如产品品质差,技术实力不足进行了分析。展望了产业未来发展趋势,并提出了增加技术投入、加强产学研协同和高端装备应用等建议。     

Sorting methods of lithium ion batteries consistency

锂离子电池因其高能量密度和长循环寿命而得到广泛应用.然而当多个电池通过串联或者并联成组时,电池组往往存在容量衰减过快,寿命较短的问题,这是由于电池单体之间的非一致性而造成的.如何利用简单,可靠的分选方法,筛选出性能尽可能一致的电池用来成组,对锂离子电池在大规模储能中的推广应用具有重要的科学与实践意义.该文综述了目前国内外锂离子电池一致性的分选方法,包括各方法的机理特点,并且简单介绍了作者课题组在这方面的研究进展.采用阻抗谱方法或许是建立准确,快速的评价体系和提高配对电池的一致性的有效分选方法.     

Hierarchical novel NiCo2O4/BiVO4 hybrid heterostructure as an advanced anode material for rechargeable lithium ion battery

Hybrid metal oxide heterostructures have been considered as ideal and potential anode materials for lithium ion batteries (LIBs) due to their better electrochemical performances, such as reversible capacity, structural stability and electronic conductivity. Herein, we have demonstrated synthesis of NiCo₂O₄/BiVO₄ heterostructures by simple hydrothermal strategy to construct hybrid xNiCo₂O₄/(1–x)BiVO₄ heterostructures with four selected compositions, that is, x = 10%, 20%, 30% and 40%. XRD shows the phases of NiCo₂O₄ and BiVO₄ and FE-SEM data revealed strong interface coupling between NiCo₂O₄ nanowires and BiVO₄ dendrites. Upon testing for electrochemical properties, the optimized composition of 30%NiCo₂O₄-70% BiVO₄ showed higher reversible capacity of 408.6 mAh/g at a constant current rate of 0.5 A/g after 1000 cycles with columbic efficiency around 99% suggesting potential electrode material for high-performance LIBs. The higher capacity is mainly attributed to the large surface area which can provide more channels and locations for fast Li ion intercalation/de-intercalation into electrode materials. Additionally, improved Li ion storage capacity with superior rate capability of BN-30 electrode could be attributed to its lower charge-transfer resistance. The dendritic and nanowire heterostructure novel system with good stable capacity for LIBs is hitherto unattempted.