全固态锂离子电池内部热输运研究前沿

本文简要阐述了全固态锂离子电池的特点及其内部热输运研究的意义.介绍并总结了国内外与正极材料、负极材料、固态电解质,以及电极与电解质界面热输运性质相关的实验和理论工作.针对脱嵌锂过程对电极材料热导率的影响机理尚不明确,非晶态转变对电极材料热输运研究的挑战,界面热输运模型与方法不足等问题,系统梳理了全固态锂离子电池内部热输运的重要前沿科学问题.     

直流道PEMFC两相流数学模型

建立直流道质子交换膜燃料电池(PEMFC)三维非等温两相流数学模型,基于质子交换膜与气体之间的水分传递特征,综合考虑电渗、浓度扩散及电化学反应作用的影响,发展了膜电极水分传递的非平衡扩散模型.并自主开发程序代码对电池内复杂的多物理场耦合传递过程进行数值模拟,研究PEMFC电极内气态水、液态水分布、质子膜含水量分布和水迁移特性等,分析单电池内部的温度分布特征,并获得电池极化性能曲线.     

LiCoO_2电池正极微结构模拟退火重构及传输物性预测

采用实验或数值方法对多孔复合电极微结构进行重构和特征化不仅是锂离子电池介观尺度数值模型的重要组成部分,也是通过数值技术由底向上进行电极微结构虚拟设计与优化的基础.本文以某商用LiCoO2电池正极的孔隙率、电极组成材料的组分体积分数、活性材料颗粒粒径分布、相关函数等重要结构与统计信息作为输入参数,采用模拟退火法对其微结构进行了数值重建,得到了明确区分活性材料、固体添加物以及孔相(电解液)的微结构,其重要特性参数与实际电极一致.对重构电极的特征化分析,得到了电极内部各组分的连通性、孔径分布等特征信息.同时,采用D3Q15格子Boltzmann模型计算了重构电极的有效热导率以及电解液(或固相)的有效传输系数.与随机行走模拟或Bruggemann等经验公式相比,基于实际电极微结构细节信息的介观数值方法对多孔电极有效传输系数的预测更为准确可靠.     

双相多孔锂离子电池液/固界面的声反射与声透射

采用传递矩阵法,同步联立改进的Biot理论,对含液固界面的双相多孔锂离子电池的超声反射与透射系数进行理论求解。考虑锂离子的摇摆特性对电极力学性能的影响,计算了对应状态下液/固界面的双相多孔锂离子电池声反射及透射系数的角度谱与频率谱。同时,构建了不同荷电状态时含单元锂离子电池的频域仿真模型,以萃取对应的超声反射及透射角度谱及频率谱,并与理论计算结果对比吻合良好。随后,以多单元锂离子电池为例,在不同的荷电状态下,分析了反射与透射系数随斜入射角度、入射波频率的变化关系,并分别指出了其角度谱及频率谱特征点随荷电状态的变化特征,为锂离子电池运行状态的超声无损测量提供了理论基础。     

基于电池热特性及产热行为的新型锂离子电池评价

建立了一种新的基于锂离子电池热特性及产热行为的电池性能评价方法. 通过测量一系列不同容量及电极材料的18650电池在不同充放电时间及电流下其充放电能量的变化,建立了一个包含焦耳热与极化热影响因子的表达电池在充放电过程中的能量损失的模型. 利用这种模型,计算出电池总内阻R以及极化参数′,并且对R及′在不同温度下的变化情况进行了研究,建立一个对不同电池和不同温度都适用的普适性模型.     

基于电化学模型的锂离子电池多尺度建模及其简化方法

锂离子电池的精确建模和状态估计对于电动汽车电池管理系统非常重要,准二维(P2D)电化学模型由于计算复杂,难以直接应用于电池管理的参数在线估计和实时控制中.本文基于多孔电极理论和浓度理论,提出一种考虑锂离子液相动力学的简化准二维(SP2D)模型.忽略锂离子孔壁流量沿电极厚度方向的变化求解SP2D模型所描述的锂离子电池锂浓度分布,基于锂离子电池电化学平均动力学行为求解固相和液相电势变化,推导出电池电压计算的简化表达式;采用恒流、脉冲以及城市循环工况放电电流对比分析了严格P2D模型与SP2D模型的终端电压和浓度分布.结果表明:SP2D模型在保持较高计算精度的同时,可显著提高计算效率.     

锂离子电池中的物理问题及其研究进展

锂离子电池作为一种性能优越的新型可充放电池已经或将要在移动通信、手提式计算机和电动汽车等诸多领域获得广泛的应用 .然而与锂离子电池相关的物理问题却往往被人们忽视 .例如 ,如何从本质上来提高正极材料的体相电子电导率 ,而不是在正极活性物质中添加炭黑之类的电子导电材料 .文章将着重针对与锂离子电池相关的物理问题 ,介绍近年来的主要进展 ,以期待对锂离子电池有更深入的了解 .     

质子交换膜燃料电池内传递现象的数值模拟

本文发展了一个质子交换膜燃料电池的三维数学模型,用于研究整个电池内的传递现象,模型全面考虑了流体 流动、热量传递、电化学动力学和多组分传递等物理化学过程。数值求解数学模型获得了电池内详细的温度、反应物浓度 和电流等的空间分布情况。为验证模型的正确性,将估算的电池性能与文献中的实验数据进行了比较。     

高功率微波土壤击穿的数值验证研究

高功率微波在土壤中传播时, 会引起土壤击穿电离而导致土壤电阻率的非线性变化, 土壤电阻率的变化又将反作用于传播过程, 加剧高功率微波衰减, 影响其能量传输效率. 通过对土壤动态电离过程的分析, 结合Maxwell方程组构建了高功率微波土壤传播模型, 采用时域有限差分法对该模型进行数值验证. 数值结果显示了高功率微波在土壤中传播、衰减等物理图像, 以及土壤电阻率的非线性变化过程. 理论分析验证了这些数值结果.     

基于扩展单粒子模型的锂离子电池参数识别策略

为了精确识别电动汽车锂离子动力电池的关键状态参数,基于多孔电极理论和浓度理论,建立了一种考虑液相动力学行为的锂离子电池扩展单粒子模型.相较于传统单粒子模型,该模型增加了对负电极表面固体电解质界面膜参数的描述,并考虑了温度和液相浓度变化对锂离子电池关键参数的耦合影响.基于所建立的扩展单粒子模型,提出一种简化的参数灵敏度分析方法和有效的锂电池参数识别策略,用以确定特定工况下的高灵敏度待识别参数,进而利用遗传算法实现参数的优化求解.最后,通过对比分析本文模型和传统单粒子模型的仿真输出电压和相同工况下电池的实验输出电压验证了提出模型和参数识别方法的有效性和可行性,为电池管理系统的健康状态估计提供了理论基础.     

纳米颗粒的表面效应和电极颗粒间挤压作用对锂离子电池电压迟滞的影响

硅作为锂离子电池电极材料之一,其应力效应尤为突出,进而将影响电池性能.本文建立了电化学反应-扩散-应力全耦合模型,并研究了恒压充放电条件下扩散诱导应力、表面效应和颗粒间挤压作用对电压迟滞的影响.结果发现,应力及其导致的电压迟滞程度与颗粒尺寸相关.在大颗粒(颗粒半径r 100 nm)中,扩散诱导应力是导致电势迟滞效应的主要因素,这将导致电池能量耗散.对于纳米级小颗粒(r 100 nm)而言,表面效应占据主导,表面效应虽然能缓解电压迟滞,同时却会使驱动电化学反应部分的过电势回线下移,造成锂化容量衰减.本文综合考虑了扩散诱导应力和表面效应,得出:半径为10 nm的颗粒将会使电极具备较好的综合性能.此外,对于硅电极而言,颗粒间挤压作用会使应力回线向压应力状态演化,进而导致锂化容量的衰减.计算结果表明,在电极设计中,对孔隙率设定下限值有助于提升电极性能.     

Square model for charge and discharge behavior of cathode electrode materials

The shape of cathode electrode affects severely the potential curves of charge/discharge process of lithium ion cells. In this paper, we take LiFePO₄ for an example. The square model is presented to predict the concentration of lithium on the cathode electrode under some simplified conditions. With the square model as a tool, effects of shape and position are determined and analyzed. Meanwhile, the lithium transportation, Gibbs free energy, and battery potential are proved to be different from that of sphere models. It shows that asymmetry of electrode materials makes a great impact on the performance of charge or discharge process.     

基于分布参数估计的锂离子电池故障预测建模

Lithium ion battery has typical character of distributed parameter system, and can be described precisely by partial differential equations and multi-physics theory because lithium ion battery is a complicated electrochemical energy storage system. A novel failure prediction modeling method of lithium ion battery based on distributed parameter estimation and single particle model is proposed in this work. Lithium ion concentration in the anode of lithium ion battery is an unmeasurable distributed variable. Failure prediction system can estimate lithium ion concentration online, track the failure residual which is the difference between the estimated value and the ideal value. The precaution signal will be triggered when the failure residual is beyond the predefined failure precaution threshold, and the failure countdown prediction module will be activated. The remaining time of the severe failure threshold can be estimated by the failure countdown prediction module according to the changing rate of the failure residual. A simulation example verifies that lithium ion concentration in the anode of lithium ion battery can be estimated exactly and effectively by the failure prediction model. The precaution signal can be triggered reliably, and the remaining time of the severe failure can be forecasted accurately by the failure countdown prediction module.     

The influence of polytetrafluorethylene reduction on the capacity loss of the carbon anode for lithium ion batteries

To date, the lithium ion battery has become the focus of secondary battery studies. A considerable capacity loss during the first lithiation of its carbon electrode is a severe drawback of this kind of battery. It has been suggested frequently that the capacity loss was caused by the decomposition of the electrolyte on the surface of the carbon electrode. However, the contribution of binder reduction to this capacity loss has never been considered until now. This paper deals with the binder polytetrafluorethylene (PTFE) reduction and finds that it plays an important part in the capacity loss. It is found that (1) the capacity loss increased with increasing PTFE binder content, (2) the X-ray diffraction peaks corresponding to the PTFE, binder became weaker, while more of the lithium was consumed by the carbon electrode, and disappeared when the consumed amount of lithium exceeded the theoretical value of 1070 mAh per gram of PTFE and (3) the height of the high voltage plateau of the electrochemical titration curves was just a function of storage time, and the length of the plateau was a function of the PTFE content.     

Generation of thermonuclear energy by fusing hydrogen and lithium atoms

A method of designing a thermonuclear reactor based on the modified Cockroft-Walton accelerator, where the lithium-proton fusion was first observed, is considered. It is proposed that the reactor have the form of a spherical capacitor with a point lithium cathode used as the inner electrode and a spherical anode, as the outer electrode. The interelectrode space is filled with hydrogen. A high-voltage electric pulse applied to the electrodes is used as a driver. The reactor parameters providing an ion temperature of 100 keV and a proton flux of 8.6×10¹⁵ W/cm² to the cathode are determined. The basic elements of a system generating thermonuclear fusion energy, including those of the energy conversion chamber with a fusion chamber inside, are listed, and possible applications of the system are indicated.     

Materials for Electrodes of Li-Ion Batteries: Issues Related to Stress Development

Presently, rechargeable Li-ion batteries, possessing highest energy densities among all batte-ries, are used in a major fraction of all portable electronic devices. However, for bestowing the Li-ion batteries suitable for such advanced applications, further improvements in the energy densities (Li-capacities) and in the cycle life are essential. In a broader sense, this can be achieved by replacing the presently used electrode materials by materials possessing higher Li-capacities and minimization of the degradation of such materials with electrochemical cycling. It has been realized that the major reason for degradation in battery performance in terms of capacity with cycling is the disintegration/fragmentation of the active electrode materials due to stresses generated during Li-intercalation/de-intercalation in every cycle. Such stresses arise from the reversible volume changes of the active electrode materials during Li-insertion and removal. In quest of higher energy densities, replacement of the presently used graphitic carbon by potentially higher capacity metallic anode materials (like Si, Sn, and Al) is likely to further accrue this stress related disintegration due to ～30 times higher volume changes experienced by such materials. It has also been recently realized that passivating layer formed on the surface of the electrodes also contributes toward the stress development. After briefly introducing the mechanistic aspects of Li-ion batteries, this article focuses on the reasons and consequences associated with stress developments in different electrode materials, highlighting the various strategies, in terms of designing new electrode com-positions or reducing the microstructural scale, that are being presently adopted to address the stress-related issues. Considering that experimental determination of such stresses is essential toward further progress in Li-ion battery research, this article introduces a recently reported technique developed for real-time measurement of such stresses. It finally concludes by raising some critical issues that need to be resolved through further research in this area.     

基于材料基因组方法的锂电池新材料开发

近年来,在锂二次电池新材料的研发过程中逐渐建立了基于材料基因组思想的高通量计算理论工具与研究平台.在该平台上,通过将不同精度的计算方法组合,实现了基于离子输运性质的材料筛选;通过将信息学中数据挖掘算法引入高通量计算数据的分析,证实了材料大数据解读的可行性.上述平台实现了在锂电池固体电解质的高通量筛选、优化和设计上进行新材料研发的示范应用,通过高通量计算筛选获得了两种可用于富锂正极包覆材料的化合物Li_2SiO_3和Li2SnO_3,有效改善了富锂正极的循环稳定性;通过对掺杂策略的高通量筛选,获得了提高固体电解质β-Li_3PS_4离子电导率和稳定性的方案;通过高通量结构预测设计了全新的氧硫化物固体电解质LiAlSO;并在零应变电极材料结构与性能的构效关系研究中进行了大数据分析的尝试,分析了零应变电极材料的设计依据.上述材料基因组方法在锂电池材料研发中的应用为在其他类型材料研发中推广这种新的研发模式提供了可能.     

Copper‐Based Nanomaterials for High‐Performance Lithium‐Ion Batteries

With the increasing energy demands for electronic devices and electrical vehicles, anode materials for lithium‐ion batteries with high specific capacity, good cyclic and rate performance become one of the focal areas of research. A class of them is the copper‐based nanomaterials that have thermal and chemical stability, high theoretical specific capacity, low price and environment friendliness. Now this kind of nanomaterials has been recognized as one of the critical materials for lithium‐ion batteries due to the predicted future market growth. Current status of different copper‐based materials which produced already are discussed. In this review, comprehensive summaries and evaluations are given in synthesis strategies, tailored material properties and different electrochemical performance. Recent progress of general copper‐based nanomaterials for lithium‐ion batteries is carefully presented.     

The first in situ 7Li NMR study of the reversible lithium insertion mechanism in disorganised carbons

We study a disordered carbon designed to be used as negative electrode in a secondary lithium battery. We perform in situ magnetic resonance, i.e. we run several electrochemical cycles inside the magnet while recording NMR spectra. We obtain simultaneous ⁷Li NMR and electrochemistry data and may thus analyse: the detailed chronology of the events, the Knight shift, the line width, the relaxation time T₁. This experimental work allows us to evidence a quasi metallic lithium, less diffusive than in metal and in graphite. The quasi metallic lithium is responsible for the very good reversible capacity, at a very low voltage. We indicate a model for the insertion/extraction of lithium in the fibers. The disordered carbon under study exhibits better qualities than graphite's for secondary battery applications. Only one drawback remains: a 0.5 V hysteresis; NMR shows that it occurs when the lasts quasi metal lithium are to be extracted. We evaluate the energy barrier.     

Design of ionic liquid-based hybrid electrolytes with additive for lithium insertion in graphite effectively and their effects on interfacial properties

To address the challenge of the IL-based electrolyte cannot be effectively intercalated in graphite anode, and especially the urgent needs for the compatibility between high performance and high security, the IL-based hybrid electrolyte systems with ethylene carbonate/propylene carbonate (EC/PC) as a co-solvent and vinylene carbonate (VC) as an additive were designed. The high dielectric constant of EC/PC significantly increased the ionic conductivity and lithium ion migration of the electrolyte system. Meanwhile, the presence of VC can form SEI preventing EC and PYR₁₄⁺ reductive decomposition on the electrode interface, and at the same moment, the SEI promotes effective Li cation insertion into the graphene interlayer. The Li/C half-cells showed high reversible capacity, cycling efficiency, and good cycle stability with the IL-based hybrid electrolyte. It is worth to highlight the better performance, in terms of the excellent thermal stability and high safety. Thus, the IL-based hybrid electrolyte combined with good electrochemical performance holds substantial promise for lithium-ion battery, and should have broad application prospects in the high energy density, especially high-security requirements, of the new lithium-ion battery.