磷酸铁锂储能电池过充热失控仿真研究

锂离子电池的热失控是导致储能电站发生起火或爆炸等安全事故的根本原因,研究锂离子电池热失控的发展规律和本征特性对于电化学储能电站的安全监测和故障预警具有重要意义。建立了磷酸铁锂储能电池在过充条件下的三维电化学-热耦合热失控的仿真模型,通过镀锂动力学方程量化过充负极镀锂量,引入SEI膜生长动力学方程反映镀锂与电解液反应速率,以量化负极镀锂与电解液反应产热,并引入其他副反应产热方程共同研究磷酸铁锂电池早期过充热失控温度变化及各副反应产热情况。分别研究了不同充电倍率(1C、2C、3C),不同环境温度(20℃、30℃、40℃)下磷酸铁锂电池热失控早期负极表面镀锂量变化、热失控温度变化曲线以及各副反应产热量变化特性,分析磷酸铁锂电池过充热失控温度发展过程及副反应产热规律。结果表明,负极镀锂与电解液反应作为过充热失控过程最起始的副反应,在电池热失控早期促使了其他副反应的开启,成为过充热失控的起始。本研究可为磷酸铁锂电池过充热失控早期过程探究提供理论参考。     

基于电化学-热耦合模型的锂离子电池组件产热分析北大核心CSCD

研究电池电化学过程产热对锂离子电池的热管理至关重要。本工作建立了三元NMC锂离子电池的电化学-热耦合模型,首先通过对该电池进行不同倍率的放电与温度实验测试,验证了该模型在电压和温度变化预测准确性。然后针对不同温度下的表现进行模拟仿真研究。在室温下,无论倍率大小,负极产热总是小于正极产热,虽然负极的极化热高于正极,但其可逆吸热较大,导致产热水平低于正极。而随着放电倍率的增加,正极产热所占比例减小,负极所占比例先增加后减小,而集流体产热所占比例持续增加。然而,低温条件下的电池放电表现出与室温情况不同的产热特性,首先,低温导致低倍率负极产热率比例大大增加,负极可逆热为总可逆热的主要贡献热。而高倍率负极产热率减少,正极则呈相反趋势。其次在低温下放电时间随倍率增加呈现不同趋势,高倍率下放电电压快速降低导致放电不完全,在低倍率0.5~1 C放电运行时出现了电压反弹现象但基本放电完全,这是由于低温限制了负极颗粒内部锂离子及时向外扩散,造成电阻增加与电压快速降低,同时大量产热导致自身温升,从而在低倍率下获得电压反弹并保持持续放电的能力。     

Reviews of selected 100 recent papers for lithium batteries(Apr. 01, 2019 to May 31, 2019)

该文是一篇近两个月的锂电池文献评述,以“lithium”和“batter*”为关键词检索了Web of Science从2019年4月1日至2019年5月31日上线的锂电池研究论文,共有2969篇,选择其中100篇加以评论。正极材料主要研究了层状三元材料、富锂相材料和尖晶石材料的结构和表面结构随电化学脱嵌锂变化以及掺杂和表面包覆及界面层改进对其循环寿命的影响。硅基复合负极材料研究侧重于复合材料、电极结构和电解液添加剂改进,金属锂负极的研究侧重于通过表面覆盖层的设计来提高其循环性能。固体电解质重点研究硫化物和含卤素的硫化物,固态电池的研究也多数选用硫化物固体电解质。电解液添加剂则重点在于提升高电压和高镍电解质循环稳定性和充放电库伦效率。锂硫电池的研究侧重于正极的改进。原位分析偏重于电极中的反应和固态电池的失效过程。理论模拟工作涵盖动力学、界面SEI形成机理分析和电池失效机制等。     

基于电化学热耦合模型的富镍锂离子电池产热分析

锂离子电池在工作过程中产生的热效应会影响其温度和电化学性能,并极大地影响电池的安全性和使用寿命.分析电池在放电过程的热特性变化规律及产热机制,评估电池内部不同性质的产热对温度变化的相互作用,对于电池热管理系统的设计起到至关重要的作用.因此,本工作以富镍三元锂离子电池为研究对象,建立了基于动态参数响应的电化学热耦合模型,...     

Theoretical study on discharge behavior of LiFePO4 battery

使用多孔电极理论对LiFePO4（LFP）锂离子电池的放电行为进行了详细探讨,发现随着放电过程进行,电极内部的电化学反应从隔膜侧向集流体侧移动,并且移动过去之后LFP基本完成放电过程,放电截止时电化学反应截止在电极的某个位置,并不是所有的LFP颗粒都完成了放电。随后对放电速率、电极电导率和电解液扩散系数对放电过程的影响进行了研究。随着放电倍率增加,电化学反应推进的距离不断减少,并且峰值不断增大,峰值区域变窄。提高电极电导率可以保证电化学反应从隔膜侧开始进行,但是继续提高电极电导率并不能进一步将电化学反应的峰值向电极深处推进。较高的扩散系数可以保证所有的活性材料都能发生电化学反应。以上结论可对高性能LFP锂离子电池的设计和制备提供了有效的指导作用。     

基于三维电化学热耦合析锂模型的锂离子电池参数设计

锂离子电池负极析锂可能会诱发热失控,进而导致安全事故。而通过优化电池设计参数能够有效减少析锂副反应的发生,因此本工作提出一种基于三维电化学热耦合析锂模型的锂离子电池参数设计优化方法。首先,将模型参数进行分类,分别采用实验、精确测量、文献查找和参数辨识等方法获取相应的参数。同时加入可逆锂重嵌入机制和产热模型,建立三维电化学热耦合析锂模型。模型建立完成后,对模型精度进行验证,验证结果表明模型可以较好地模拟电池在常温和低温下端电压的变化,并且能够定量描述在低温大倍率充电期间电池内部的析锂程度、温度分布等非均一现象。最后,通过分析电极尺寸和极耳位置,研究电池设计参数对非均一析锂的影响。仿真结果表明：电极长度增加会导致电极区域温度差异和电流密度的不一致性增大,综合影响下使电池析锂时间略有提前,但对电池总体析锂程度影响较小;电池极耳位置处于长度方向的轴线对侧时能够有效缓解负极析锂,相对析锂程度降低了16.7%。     

Reviews of selected 100 recent papers for lithium batteries (Apr. 1, 2018 to May 31, 2018)

该文是一篇近两个月的锂电池文献评述,以"lithium"和"batter^*"为关键词检索了Web of Science从2018年4月1日至2018年5月31日上线的锂电池研究论文,共有1807篇,选择其中100篇加以评论。正极材料主要研究了三元材料、富锂相材料和尖晶石材料的结构和表面结构随电化学脱嵌锂变化以及掺杂和表面包覆及界面层改进对其循环寿命的影响。硅基复合负极材料研究侧重于电极结构和电解液添加剂改进,金属锂负极的研究侧重于通过表面覆盖层的设计来提高其循环性能。电解液添加剂、固态电解质电池、锂硫电池的论文也有多篇。原位分析偏重于固态电池的界面,理论模拟工作涵盖储锂机理、动力学、界面SEI形成机理分析和固体电解质等。除了以材料为主的研究之外,还有多篇关于电池分析的研究论文。     

凝胶型锂离子电池的制作及电化学和安全性能

采用原位聚合法制备了凝胶型软包锂离子电池,该电池包括钴酸锂正极、石墨负极、镀陶瓷聚乙烯隔膜,以及弥散于正负极和隔膜之间的凝胶电解质.电化学测试表明,凝胶型电池具有和液态电池可比的容量和循环稳定性.差示扫描量热(DSC)测试表明,相对于液态电解质,凝胶电解质与钴酸锂正极和石墨负极之间的热稳定性更好.热板和加速量热(ARC...     

锂离子电池不同服役工况下失效研究进展

锂离子电池在长期服役时极易出现失效现象,包括内阻增大、容量衰减、析锂、产气等,其失效过程难以监测,容易导致锂离子电池的安全性、可靠性和使用寿命严重降低。通过研究搁置、长循环及浮充等不同服役工况下电池的失效原因,了解电池失效机制,可以快速监测电池的健康状态和服役寿命。本文对不同服役工况下电池失效的相关研究进行探讨,综述了在不同温度、电压和荷电状态等条件下服役时,锂离子电池内部正极、负极、隔膜和电解液的失效机理,着重介绍了电池在不同电压和温度下的搁置性能、搁置下的失效模型、长循环后正负极结构的变化、高温浮充后的失效机制及产气机理。同时也有针对性地提出了锂电负极材料、隔膜、电解液及正极材料等相关要素的优化方案。综合分析表明电极中活性锂的损失、活性物质的损失、颗粒的破裂、过渡金属的溶出、固体电解质界面膜（SEI）分解等都会引起锂离子电池的失效。减小颗粒粒径、加入电解液成膜添加剂以及优化隔膜的穿透性等,有望降低锂离子电池在长期服役过程中的失效速率,确保锂离子电池安全稳定运行。     

Experimental measurement and analysis methods of cyclic voltammetry for lithium batteries

循环伏安作为一种重要的电化学测试方法,在电化学领域尤其是锂电池的研究中有着广泛的应用,常用于电极反应可逆性、电极反应机理及电极反应动力学参数的研究。本文介绍了循环伏安的基本原理、测试方法以及常用仪器,并结合实际案例,具体分析了循环伏安在锂电池电极材料反应机理、电极过程动力学以及电解液电化学稳定性方面的应用研究。     

Combustibility and hazard of lithium iron phosphate power battery components in different aging states

选用四种衰退状态,容量保持率（capacity retention ratio,CRR）分别为100%、85%、75%及65%的磷酸铁锂动力电池为研究对象,采用锥形量热仪（CONE）对电池关键组件（含电解液的正极片、负极片及隔膜）的燃烧性和生烟性进行了研究,并运用层次分析法（analytic hierarchy process,AHP）综合评价了不同衰退状态电池组件的火灾危险性。结果表明,随着电池容量保持率的下降,电池组件中负极的有效燃烧热值有所下降,并且电池组件的CO₂产率和总生烟量逐渐降低;容量保持率100%~85%的电池组件的归一化危险性指数要明显大于75%~65%的电池组件。     

Study on electrochemical and thermal characteristics of lithium‐ion battery using the electrochemical‐thermal coupled model

The higher specific energy leads to more heat generation of a battery, which affects the performance and cycle life of a battery and even results in some security problems. In this paper, the capacity calibration, Hybrid Pulse Power Characteristic (HPPC), constant current (dis)charging, and entropy heat coefficient tests of chosen 11‐Ah lithium‐ion batteries are carried out. The entropy heat coefficient increases firstly and then decreases with the increase of the depth of discharge (DOD) and reaches the maximum value near 50% DOD. An electrochemical‐thermal coupled model of the chosen battery is established and then verified by the tests. The simulation voltage and temperature trends are in agreement with the test results. The maximum voltage and temperature error is within 2.06% and 0.4°C, respectively. Based on the established model, the effects of adjustable parameters on electrochemical characteristic are systematically studied. Results show that the average current density, the thickness of the positive electrode, the initial and maximum lithium concentration of the positive electrode, and the radius of the positive electrode particle have great influence on battery capacity and voltage. In addition, the influence degree of the internal resistance of the solid electrolyte interface (SEI) layer, the thickness of negative electrode, and the initial and maximum lithium concentration of the negative electrode on the capacity and voltage is associated with certain constraints. Meanwhile, the influences of adjustable parameters related to thermal characteristic are also systematically analyzed. Results show that the average current density, the convective heat transfer coefficient, the thickness, and the maximum lithium concentration of the positive electrode have great influence on the temperature rise. Besides, the uniformity of the temperature distribution deteriorates with the increase of the convective heat transfer coefficient.     

A hybrid power source with a shared electrode of polyaniline doped with LiPF6

We fabricated a hybrid power source device with three electrodes of which one was a LiPF₆-doped polyaniline (PAn) electrode playing the roles of both the positive electrode of a lithium secondary battery and an electrode of a redox supercapacitor. As a consequence, the shared electrode acts as a positive electrode or a positive terminal of a hybrid power source. The negative terminal was connected between a lithium metal electrode and another LiPF₆-doped PAn electrode. After characterizing and comparing this hybrid power source with a single lithium secondary battery, its discharge performance was superior to that of a single lithium secondary battery when adopting the sheet-type PAn-LiPF₆ electrodes and the porous separator as an electrolyte medium. In this case, the hybrid power source was shown to be advantageous in the high pulse mode of discharge.     

Effect of electrode physical and chemical properties on lithium‐ion battery performance

The effect of physical and chemical properties on the performance of both positive and negative electrodes is studied for lithium‐ion (Li‐ion) batteries. These properties include the lithium diffusivity in the active electrode material, the electrical conductivity of the electrode, and the reaction rate constant at electrode active sites. The specific energy and power of the cells are determined at various discharge rates for electrodes with different properties. In addition, this study is conducted across various cell design cases. The results reveal that at moderate discharge rates, lithium diffusivity in the active negative‐electrode material has the highest impact on cell performance. The specific energy and power of the cell are improved ~11% by increasing the lithium diffusivity in the active negative‐electrode material by one order of magnitude. Around 4% improvement in the cell performance is achieved by increasing the reaction rate constant at the active sites of either electrodes by one order of magnitude. Copyright © 2013 John Wiley & Sons, Ltd.     

A model for the silver–zinc battery during high rates of discharge

A transient one-dimensional mathematical model is developed and used to study the performance and thermal behavior of the silver–zinc cell during discharge. The model considers the negative (zinc) electrode, separator, and positive (silver) electrode and describes the simultaneous electrochemical reactions in the positive electrode, mass transfer limitations, and heat generation. Changes in porosity and electrolyte composition due to electrochemical reactions, local reaction rates, diffusion, and migration of electrolyte are reported. Emphasis is placed on understanding the movement of the reaction front in the negative electrode during discharge and its correlation to the useful capacity of the cell. The sensitivity of this capacity to changes in the values of initial electrolyte, exchange current densities, and tortuosity are presented. It is shown that under certain conditions, in a system employing 25% KOH as the electrolyte, the useful capacity of the cell could be limited to 55.6% of its rated capacity when the discharge rate is increased from 1C to 2C. The temperature rise in a single cell was predicted and observed to agree with the experimental values.     

Polymers for advanced lithium-ion batteries: State of the art and future needs on polymers for the different battery components

Polymers have been successfully used as electrode compounds and separator/electrolyte materials for lithium ion batteries (LiBs) due to their inherent outstanding properties such as low-density, easy of processing, excellent thermal, mechanical and electrical properties and easily tailored functional performance matching the final device requirements. Battery performance strongly depends on the polymer type used. The physico-chemical properties of the polymers that are being used as different battery components need to be further improved to boost the development of the next generation of batteries for the electric vehicle industry, where increased energy density and safety are required. Considering its role in LIBs, this review summarizes the latest advances in the field of polymers applied as electrode compounds and separator/electrolytes. For each battery component, the state-of-art is divided by polymer type. Current bottlenecks and challenges that face polymers in LIBs are shown, and possible strategies to face them are provided.     

Ambient operation of Li/Air batteries

In this work, Li/air batteries based on nonaqueous electrolytes were investigated in ambient conditions (with an oxygen partial pressure of 0.21 atm and relative humidity of ∼20%). A heat-sealable polymer membrane was used as both an oxygen-diffusion membrane and as a moisture barrier for Li/air batteries. The membrane also can minimize the evaporation of the electrolyte from the batteries. Li/air batteries with this membrane can operate in ambient conditions for more than one month with a specific energy of 362 Wh kg⁻¹, based on the total weight of the battery including its packaging. Among various carbon sources used in this work, Li/air batteries using Ketjenblack (KB) carbon-based air electrodes exhibited the highest specific energy. However, KB-based air electrodes expanded significantly and absorbed much more electrolyte than electrodes made from other carbon sources. The weight distribution of a typical Li/air battery using the KB-based air electrode was dominated by the electrolyte (∼70%). Lithium metal anodes and KB-carbon account for only 5.12% and 5.78% of the battery weight, respectively. We also found that only ∼20% of the mesopore volume of the air electrode was occupied by reaction products after discharge. To further improve the specific energy of the Li/air batteries, the microstructure of the carbon electrode needs to be further improved to absorb much less electrolyte while still holding significant amounts of reaction products.     

Review of research on heat generation characteristics during charging and discharging of lithium ion batteries

电动车辆的性能和成本很大程度上取决于动力电池组的性能和使用寿命,而电池组的性能和使用寿命又受到电池单体产热的影响。研究锂离子电池充放电过程中的产热特性及影响因素,对锂电池的开发及使用具有指导意义。本文从环境温度、充放电倍率、电池材料、荷电状态和老化程度五个方面入手,综述了各因素对锂离子电池产热的影响。     

新型PEO/LPOS复合聚合物电解质的制备与性能研究

将具有较高电导率和稳定性的硫化物电解质LPOS引入PEO基聚合物中,制备一种新型PEO/LPOS复合聚合物电解质。研究结果表明,1%LPOS的添加能显著改善PEO基聚合物电解质的电导率、锂离子迁移数和电化学稳定性。与纯PEO基电解质相比,新制备的复合聚合物电解质PEO18-LiTFSI-1%LPOS室温电导率由   6.18×106 S/cm提高至1.60×105 S/cm,提高了158%。80 ℃表现出最佳电导率为1.08×103 S/cm,电化学窗口提高至4.7 V,同时具有非常良好的对锂稳定性。以新型复合电解质组装的LiFePO4/Li全固态锂电池表现出良好的循环稳定性,在60 ℃ 1 C下循环50周后放电比容量仍维持在105 mA•h/g以上。