基于电化学-热耦合模型研究隔膜孔隙结构对锂离子电池性能的影响机制

隔膜孔隙结构对锂离子电池性能具有重要的影响,本文提出了可准确描述充放电过程中锂离子电池内部复杂物理化学现象的电化学-热耦合模型,发现该模型较文献中模型的计算结果更接近实验测试数据.利用该模型探讨了隔膜孔隙率与扭曲率分别对锂离子电池性能的影响规律,发现减小孔隙率或增大扭曲率,电池输出电压、最大放电容量和平均输出功率均不断降低,电池表面温度和温升速度均不断升高;当孔隙率减小或扭曲率增大到一定程度时,放电初期电池输出电压均会出现先下降后回升的现象,且孔隙率越小或扭曲率越大,其下降的幅度越大、速度越快,回升所需时间也越长;要确保其不低于截止电压,隔膜扭曲率必须小于临界扭曲率(其下降至最低点刚好等于截止电压时的隔膜扭曲率).综合分析了放电过程中电池内部各电化学参量和产热量的动态分布规律,发现隔膜孔隙率和扭曲率主要影响放电末期电极膜片内部电化学反应以及其他放电时刻电解液中有效Li~+扩散(传导)系数.     

A dynamic capacity fading model with thermal evolution considering variable electrode thickness for lithium-ion batteries

Capacity is one of the key parameters to characterize the performances of lithium-ion batteries. Heat generation analysis is essential to evaluate the safety of batteries. To figure out the effects of electrode thickness on capacity fade and thermal behaviors, a capacity fading model is proposed considering reaction kinetics and mass transfer processes on solid electrolyte interface (SEI) layers coupled with thermal evolution. Simulations are conducted on seven LiFePO₄ batteries with variable electrode thicknesses. Results show that, with the increase of electrode thickness, the capacity losses of batteries deteriorate, and the total heat generation aggravates. For the battery with thick electrode, both the polarization overpotential and the gradient of lithium ion concentrations on particle surfaces of active materials increase on the edges, and then decrease perpendicularly to the cathodes. Under the adiabatic conditions, the temperature of battery (with anode 68 μm and cathode 140 μm) is increased to over 130 °C at the sixth cycle. The temperature of batteries declines when discharging in the beginning and then rises, which is noticeable for the batteries with thin electrodes. The proposed model and the simulation results would provide deep insights into both design and operation of batteries.     

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。     

多层多孔锂离子电池结构的导波频散特征及其应用EI北大核心CSCD

采用状态矩阵与勒让德级数联合法,同步联立Biot理论,构建多层多孔锂离子电池声传播特性理论模型,以厚1.9 mm软包钴酸锂电池为例,数值分析了荷电状态(State of Charge,SOC)对多模态频散曲线的影响规律。同时,建立了电池中的声传播特性频域仿真模型,提取频域仿真中的超声导波频散曲线。此外,以体积小、柔性强的压电纤维复合材料(Macro Fiber Composite,MFC)为基础,实验探究了不同SOC对锂离子电池中声学行为的影响。采用互相关分析获取电池放电过程中声波渡越时间的偏移规律,建立了1.9 mm软包钴酸锂电池的声学波动行为与电池SOC间的映射关系。     

电动汽车锂离子电池热管理系统研究进展

锂离子电池作为电动汽车最广泛使用的动力源,对工作温度高度敏感,为保证其高性能和安全运行,电池热管理系统必不可少.本文综述了近年来锂离子电池热管理系统的研究进展.首先讨论了由高低温环境和电池温度不均匀引起的临界热问题.在此基础上,对设计原则和现有的电池热管理系统进行了广泛的介绍和阐述.然后进一步分析了用于未来电池热管理系统的热电器件和内部加热方法等新兴技术.分析表明,被动和主动冷却/加热方法的组合有望满足苛刻的热要求,特别是在功率波动剧烈的动态条件下.此外,电池在变工况下所输出的电流、电压等均不相同,因此建议对电动汽车动力电池进行动态性能实时管理,从而延长电池使用寿命。     

Redox-assisted Li~+-storage in lithium-ion batteries

Interfacial charge transfer is the key kinetic process dictating the operation of lithium-ion battery. Redox-mediated charge propagations of the electronic(e-and h~+) and ionic species(Li~+) at the electrode–electrolyte interface have recently gained increasing attention for better exploitation of battery materials. This article briefly summarises the energetic and kinetic aspects of lithium-ion batteries, and reviews the recent progress on various redox-assisted Li~+storage approaches.From molecular wiring to polymer wiring and from redox targeting to redox flow lithium battery, the role of redox mediators and the way of the redox species functioning in lithium-ion batteries are discussed.     

Analysis on the capacity degradation mechanism of a series lithium-ion power battery pack based on inconsistency of capacity

The lithium-ion battery has been widely used as an energy source. Charge rate, discharge rate, and operating tem- perature are very important factors for the capacity degradations of power batteries and battery packs. Firstly, in this paper we make use of an accelerated life test and a statistical analysis method to establish the capacity accelerated degradation model under three constant stress parameters according to the degradation data, which are charge rate, discharge rate, and operating temperature, and then we propose a capacity degradation model according to the current residual capacity of a Li-ion cell under dynamic stress parameters. Secondly, we analyze the charge and discharge process of a series power battery pack and interpret the correlation between the capacity degradations of the battery pack and its charge/discharge rate. According to this cycling condition, we establish a capacity degradation model of a series power battery pack under inconsistent capacity of cells, and analyze the degradation mechanism with capacity variance and operating temperature difference. The comparative analysis of test results shows that the inconsistent operating temperatures of cells in the series power battery pack are the main cause of its degradation; when the difference between inconsistent temperatures is narrowed by 5 ℃, the cycle life can be improved by more than 50%. Therefore, it effectively improves the cycle life of the series battery pack to reasonably assemble the batteries according to their capacities and to narrow the differences in operating temperature among cells.     

锂离子动力电池高倍率充放电过程中弛豫行为的仿真

基于电化学热耦合模型研究了动力锂离子电池高倍率充放电过程中的弛豫行为, 分析对比了不同充放电机制对电池弛豫行为的影响. 研究发现: 充放电过程中, 欧姆极化是造成电压骤变的主要原因; 而恒流-恒压的充电模式能够缓慢消除欧姆极化, 避免电池电压的骤变; 利用恒流恒压对电池进行充电能够充进更多的电量, 有利于电池性能的完全发挥; 固相锂离子浓度的弛豫时间比液相锂离子浓度的弛豫时间长, 并且在放电后期, 固相扩散的特征时间与液相扩散特征时间的比值不断增大, 固相扩散造成的极化在整个放电过程不可忽略.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/poly(ethylene terephthalate) composite separator for high-safety lithium-ion batteries

Separators have garnered substantial attention from researchers and developers in regard to their crucial role in the safety of lithium-ion batteries. In this study, a composite separator was prepared by coating cubic Al₂O₃ nanoparticles on non-woven poly(ethylene terephthalate) (PET) via a simple dip-coating process. The basic properties of the Al₂O₃-coated PET non-woven composite separator were characterized by scanning electron microscopy and other specific measurements in respect to its morphology, porosity, electrolyte wettability, and thermal shrinkage as well as its application in lithium-ion batteries. We found that the composite separator has outstanding thermostability, which may improve battery safety. Additionally, by comparison against the commercial Celgard 2500 separator, the proposed composite separator exhibits higher porosity, superior electrolyte wettability, and higher ionic conductivity. More importantly, the lithium-ion battery assembled with this composite separator shows better electrochemical performance (e.g., cycling and discharge C-rate capability) compared to that with the Celgard 2500 separator. The results of this study represent a simple approach to preparing high-performance separators that can be used to enhance the safety of lithium-ion batteries.     

A heatproof separator for lithium-ion battery based on nylon66 nanofibers

The safety of lithium-ion battery is closely related to the anti-shrink and heatproof stability of the separator. In this paper, electrospun nylon66 (PA66) nanofiber-based membrane is used as lithium-ion battery separator, showing good thermodynamics properties via thermogravimetric analysis (TG), thermal shrinkage experiment, and tension test. Furthermore, electrospun nylon66 separator based battery exhibits better safety than the battery applying Celgard commerce separator under the condition of high temperature and severe vibration. Meanwhile, the electrochemical properties of both batteries are nearly identical. These facts prove that the electrospun nylon66 separator is an ideal separator candidate for power lithium-ion battery of electric vehicles. In addition, the nylon66 separator annealed in the air has higher tensile strength and better property of elongation than the unannealed one.     

超短激光打孔中快速相变的格子玻尔兹曼模拟

采用双重分布函数的格子玻尔兹曼模型，对单脉冲激光金属打孔过程中的快速相变传热进行研究.模型考虑了金属材料熔化后熔体的流动换热，并采用浸没移动边界方案对过程中的固液界面进行追踪.采用纯导热模型和考虑对流的换热模型计算，将结果和试验进行对比，结果表明：在激光打孔过程中熔体的流动对相变传热产生较大影响，采用考虑流动换热模型的结果与实验更接近.进而对熔化速度、熔化深度以及温度场的变化进行分析，并探讨不同激光工艺参数对相变过程的影响.模拟发现一个脉冲结束后，激光的脉宽越大，孔深越小，孔径越大，且最高温度较短脉冲激光越低.     

金属橡胶热物理性能理论与试验研究

针对金属橡胶材料在高温环境下的热稳定性能和热传导性能, 基于金属橡胶的内部基本组分以及特殊的编织制作工艺, 构建了两种典型排列微元体结构, 并以此描述微元体在三种接触状态下的热膨胀特性, 提出了金属橡胶热膨胀Schapery分析模型, 从理论上解释了金属橡胶热膨胀的产生机理.根据金属橡胶基本组成单元的传热模式, 研究了金属橡胶的传热过程.利用热电比拟法和有限元法, 分析微元体的导热性能, 结合微元体的分布形式, 提出了金属橡胶的导热分析模型.试验测试了不同相对密度金属橡胶的热膨胀和热传导性能, 验证了金属橡胶热膨胀和导热特性分析理论模型的适用性.所得到的金属橡胶的热膨胀和热传导性能理论模型和试验结果, 为金属橡胶材料在高温环境下的热物理特性分析提供了理论基础和计算分析依据. 关键词： 金属橡胶 热膨胀 热传导 金属丝螺旋卷     

Analysis of Li distribution in ultrathin all-solid-state Li-ion battery (ASSLiB) by neutron depth profiling (NDP)

Lithium-ion batteries are promising energy storage technology devices. They possess many advantages, including high energy density, flexible and lightweight construction and considerable durability. The rapid development of nanotechnologies can further improve their capacity, cycle life and safety. In this experiment, Li-ion diffusion in an all-solid lithium-ion battery (ASSLiB) was studied using the Neutron Depth Profiling (NDP) nuclear analytical technique. The thin ASSLiB system was synthesised by RF magnetron sputtering. The experiment showed that NDP is a very efficient experimental tool for direct analysis of Li distribution in Li batteries. It has been found that the depth profile of Li strongly depends on the state of charge of the battery. About one-third of the total number of Li in ASSLiB can move between the electrodes during charging / discharging. It has been also shown, using the multipixel detectors, that the lateral distribution of Li in ASSLiB is not homogeneous. This can mean, for example, that the position of Li is affected by structural defects that may arise due to variation of the volume or stress of the battery during charging or discharging. In the work are presented first results of measurements performed on ASSLiB of a 1?µm thickness.     

Interfacial transport in lithium-ion conductors

Physical models of ion diffusion at different interfaces are reviewed. The use of impedance spectroscopy(IS), nuclear magnetic resonance(NMR), and secondary ion mass spectrometry(SIMS) techniques are also discussed. The diffusion of ions is fundamental to the operation of lithium-ion batteries, taking place not only within the grains but also across different interfaces. Interfacial ion transport usually contributes to the majority of the resistance in lithium-ion batteries. A greater understanding of the interfacial diffusion of ions is crucial to improving battery performance.     

Fractional Cattaneo heat equation in a semi-infinite medium

To better describe the phenomenon of non-Fourier heat conduction, the fractional Cattaneo heat equation is introduced from the generalized Cattaneo model with two fractional derivatives of different orders. The anomalous heat conduction under the Neumann boundary condition in a semi-infinity medium is investigated. Exact solutions are obtained in series form of the H-function by using the Laplace transform method. Finally, numerical examples are presented graphically when different kinds of surface temperature gradient are given. The effects of fractional parameters are also discussed.     

基于拓展分离变量法的层合材料瞬态传热分析

层合材料各层热物理参数不同,难以用常规的分离变量法求解.针对此问题对常规分离变量法进行了拓展,将层合材料受热时的温度场在时间域上分成微小时间段,在每个微小时间段内层合材料交界处的温度可认为随时间正比变化,并假设比例系数,此时在微小时间段内对各层分别利用分离变量法单独求得解析解,根据交界处温度相等能量连续的关系可求出比例系数,进而求出该微小时间段内的温度场,通过循环求解可得整个时间段内的温度场.之后,利用拓展的分离变量法对常用层合隔热材料瞬态传热进行了分析,通过与有限元方法计算的结果比较,验证了本文方法的正确性,分析了隔热材料类型、厚度,材料表面对流换热系数,空气温度等参数对隔热效果的影响.拓展分离变量法利用解析的方式求解了层合材料瞬态传热问题,物理意义比常规的数值方法明确,计算效率也较高.     

Melt Crystallization Behavior of Injection-Molded High-Density Polyethylene Based Upon a Solidification Kinetic Analysis

Rheological characterization and an in-situ temperature measurement were carried out to investigate the solidification behavior and crystallization kinetics of injection-molded (IM) high-density polyethylene (HDPE) samples. The temperature profiles obtained via the enthalpy transformation method (ETM) were also used to disclose the effect of cooling rate on the solidification kinetics during the IM process. A four parameter model (FPM) was developed in the present work, based on a three-parameter model (TPM) we proposed previously, with the FPM shown to have an obviously better fitting effect. It was seen that heat transfer at locations χ?≤?0.5 was primarily dominated by a thermal conduction mechanism, which was unlike the situation when χ?>?0.5, with χ being the fractional distance from the mold surface to the center. The results of the present study are suggested to be of significance to further research on the correlation between microstructures and properties of IM products.     

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.     

气粒两相流传热问题的光滑离散颗粒流体动力学方法数值模拟

在气粒两相流动问题中,颗粒间以及气体与颗粒间的传热问题不可忽略.光滑离散颗粒流体动力学(SDPH)模型作为一种新的求解气粒两相流动问题的方法,已经成功应用于模拟风沙运动等问题.在此基础上,提出了SDPH方法的热传导模型,模拟了气粒两相流动问题中的热传导过程以及颗粒蒸发过程.首先引入各相的能量方程,利用有限差分与光滑粒子流体动力学一阶导数相结合的方法,处理各相内部热传导项中的二阶导数问题,基于气粒两相间温度差及对流换热系数计算颗粒与气体间的热传导量,推导得到了含热传导模型的气粒两相流SDPH计算方程组,模拟计算了圆盘形颗粒团算例及鼓泡流化床内部热传导算例,并与双流体模型计算结果进行对比,结果基本符合;其次利用离散液滴模型中的颗粒蒸发传质传热定律计算颗粒的蒸发过程,数值模拟了颗粒射流蒸发过程,并与离散颗粒模型结果进行对比,两者符合得较好,验证了该方法的准确性及实用性.     

Numerical Simulation of the Non-Fourier Heat Conduction in a Solid-State Laser Medium

A hyperbolic model of non-Fourier heat conduction with non-uniform heat source is used to simulate the transient heat transfer in a high-pulse-pumped solid-state laser medium. The temperature fields are numerically analysed using the finite difference method combined with the TDMA algorithm for different pump power densities, pulse durations, thermal relaxation time and cooling intensities, respectively. The calculated results are compared with those predicted by the parabolic heat conduction model based on the Fourier law. The results indicate that the non-Fourier heat conduction phenomenon in laser media should be considered when the pump power density exceeds 104 W/m^2 or under low pulse duration. In addition, the conditions of non-Fourier effects and their influencing factors are analysed.