A comparative study on the degradation behaviors of overcharged lithium-ion batteries under different ambient temperatures

In the current work, a series of experiments are carried out to investigate the degradation behavior of lithium-ion batteries during overcharge cycling, as well as the influence of ambient temperature on the degradation. In which, different charge cut-off voltages (4.5, 4.8, and 5.0 V) and ambient temperatures (0°C, 20°C, 50°C, and 70 °C) are included. During the overcharge process, the batteries demonstrate severe temperature rises, and several key electrochemical parameters such as the charge capacity, energy density, median voltage, and resistances all increase, revealing the deterioration of heat generation and electrode kinetics. Besides that, batteries exhibit serious degradation behavior during the overcharge cycling, which is presented through the evolution of battery temperature curves, charge voltage curves, and internal resistance curves. Moreover, the severity of degradation exacerbates with the increasing overcharge degree. Finally, it is found that deep-overcharged batteries may be more sensitive to the ambient temperature than slight-overcharged ones, where an abusive temperature can significantly aggravate the corresponding degradation.     

Modeling the capacity degradation of LiFePO4/graphite batteries based on stress coupling analysis

A coupling-analysis-based model to predict the capacity degradation of LiFePO₄ batteries under multi-stress accelerated conditions has been developed. In this model, the joint effect on the battery capacity degradation of any 2 out of 5 stress factors, which include ambient temperature, end of discharge and charge voltage (EODV and EOCV), and discharge and charge rate, is studied through coupling validation tests. Coupling generally exists among these 5 stress factors, and the coupling intensity has a certain relationship with the stress levels. There is a critical stress level at which the coupling can be considered negligible, and when the stress level goes higher, coupling aggravates battery degradation exponentially. Additionally, the study also indicates that battery life shows stronger sensitivity to discharge rate and EOCV than to charge rate and EODV. The developed capacity degradation model based on the input of real operating conditions and coupling intensity calibration achieves error less than 15% when the cycling goes into the stable decay period, and the error converges gradually as the cycling continues.     

Experimental investigation on the essential cause of the degrading performances for an overcharging ternary battery

Ternary power batteries, as the mainstream power sources of electric vehicles, are liable to inducing thermal runaway (TR) with respect to their sensitivity to abusive conditions. Among various abuse conditions, the overcharge of a battery has been considered as the most common and severe case giving rise to thermal safety accidents. In this study, an overcharged battery and a normal battery, both using ternary/graphite electrodes, were investigated and analyzed synergistically through thermal behaviors and electrochemical characteristics. Initially, a series of electrochemical parameters including charge and discharge voltage plateaus, discharged capacity and time at different discharge rates, and internal resistances were carried out. Then, the heat generation behaviors between normal and overcharged batteries were evaluated. Furtherly, the interconnectedness with the electrochemical capacity degradation and heat generation aggravation of the ternary battery after overcharge was analyzed. Besides, the essential causes of the deterioration of electrochemical properties and severe heat behaviors resulting from overcharge were intensively analyzed via microscopic perspectives. In addition, the electrochemical characteristics fading of abused ternary battery triggered by overcharge were investigated, especially under higher temperature (55°C) and ultralow temperature (−20°C) conditions. Therefore, for an overcharged battery, this research not only elaborates the essential causa of the degraded electrochemical and anabatic thermal performance from a materials and thermal science perspective but also provides a foundation for further promoting the safety properties of commercialized power batteries with ternary chemical systems.     

Thermal modeling of a cylindrical LiFePO4/graphite lithium-ion battery

A lumped-parameter thermal model of a cylindrical LiFePO₄/graphite lithium-ion battery is developed. Heat transfer coefficients and heat capacity are determined from simultaneous measurements of the surface temperature and the internal temperature of the battery while applying 2 Hz current pulses of different magnitudes. For internal temperature measurements, a thermocouple is introduced into the battery under inert atmosphere. Heat transfer coefficients (thermal resistances in the model) inside and outside the battery are obtained from thermal steady state temperature measurements, whereas the heat capacity (thermal capacitance in the model) is determined from the transient part. The accuracy of the estimation of internal temperature from surface temperature measurements using the model is validated on current-pulse experiments and a complete charge/discharge of the battery and is within 1.5 °C. Furthermore, the model allows for simulating the internal temperature directly from the measured current and voltage of the battery. The model is simple enough to be implemented in battery management systems for electric vehicles.     

Analysis of the effect of resistance increase on the capacity fade of lithium ion batteries

Lithium ion cells, when cycled, exhibit a two‐stage degradation behavior characterized by a first linear stage and a second nonlinear stage where degradation is rapid. The multitude of degradation phenomena occurring in lithium ion batteries complicates the understanding of this two‐stage degradation behavior. In this work, a simple and intuitive model is presented to analyze the coupled effect of resistance growth and the shape of the state of charge (SOC)‐open circuit voltage (OCV) relationship in representing the complete degradation behavior. The model simulations demonstrate that a single resistance that increases linearly on cycling can capture the transition from slow to fast degradation, primarily due to the shape of the SOC‐OCV curve. Further, the model simulations indicate that the shape of the degradation curve depends strongly on the magnitude of current at the end of discharge of the cycling protocol. To verify these observations, specific experiments are designed with minimal capacity loss but with shrinking operating voltage ranges that result in shrinking operating OCV range. The results of the experiments validate the observations of model simulations. Further, long‐term cycling experiment with a commercial lithium ion cell shows that the operating OCV range shrinks substantially with aging and is a major reason for the observed accelerated degradation. The analysis of the present work provides significant insights towards developing simple semiempirical models suitable for battery life management in microcontrollers.     

Investigation of solid electrolyte interfacial layer development during continuous cycling using ac impedance spectra and micro-structural analysis

The formation of passivating surface films on the electrodes of a lithium-ion polymer battery was investigated at various cycling state using ac impedance spectroscopy and scanning electron microscopy (SEM). A sealed commercial cell (Sony Co.) with a nominal capacity of 840 mAh was used for the experiment. An equivalent circuit used to model the impedance spectra show that, with continuous cycling there is a relatively large increase in the interfacial impedance and charge transfer resistances after a few hundred charge–discharge cycles. It was observed that the cell capacity decrease with increase cell impedance. SEM analysis on the electrodes shows that during continuous charge–discharge cycling, the deposition of sub-micro-size particles and dissolution of surface films on the graphite surface. This observation is consistent with increase in cell impedance as a function of charge/discharge cycling.     

Dynamic model of a lead acid battery for use in a domestic fuel cell system

This paper presents a review of existing dynamic electrical battery models and subsequently describes a new mathematical model of a lead acid battery, using a non-linear function for the maximum available energy related to the battery discharge rate. The battery state of charge (SOC) is expressed in a look-up table relative to the battery open circuit voltage (VOC). This look-up table has been developed through low discharge experiments of the battery modelled. Further, both the internal resistance and self-discharge resistance of the battery are subsequently expressed as functions of the open circuit voltage. By using an electrical model with these characteristics and a temperature compensation element to model different rates of charge and discharge, a relatively simple and accurate battery model has been developed.The new model takes into account battery storage capacity, internal resistance, self-discharge resistance, the electric losses and the temperature dependence of a lead acid battery. It is shown in this paper how the necessary parameters for the model were found. The battery modelled was a Hawker Genesis 42 Ah rated gelled lead acid battery.The simulation results of the new model are compared with test data recorded from battery discharge tests, which validate the accuracy of the new model.     

The behaviour of the coup de fouet of valve-regulated lead–acid batteries

This paper presents the results of an investigation into the initial stage of the discharge voltage response of valve-regulated lead–acid (VRLA) batteries. This region is dominated by the phenomenon known as the coup de fouet which manifests itself as a voltage dip followed by a recovery. The research focuses on two parameters found within the coup de fouet region, namely, the trough and the plateau voltage. It is found that these parameters are influenced by the operating conditions and the sate-state-of health (SoH) of the battery. The operating conditions considered are discharge rate, ambient temperature, depth of previous discharge, charge duration, and float voltage. The coup de fouet parameters corresponding to high rate discharges, as well as discharges conducted at low temperatures, have reduced magnitudes compared with those conducted at lower rates or higher temperatures. This behaviour mirrors the availability of capacity when the battery is discharged under the same operating conditions. The float voltage is found to have a direct relationship with the trough and plateau voltages, whereas an indirect relationship between charge duration and the trough and plateau voltages is observed. The influence of variations in discharge depth on the coup de fouet is more complex. For consecutive discharge depths below approximately 10% of rated capacity, the coup de fouet becomes distorted and exhibits a second voltage dip. For consecutive discharges of greater depth, this does not occur. The influence of the degradation in battery SoH due to accelerated thermal ageing, water replenishment post-accelerated thermal ageing, and field ageing is investigated. The coup de fouet parameters associated with the discharge of batteries with low SoH have a reduced magnitude compared with those associated with the discharge of batteries with a high SoH.     

Improving photovoltaic system sizing by using electrolyte circulation in the lead-acid batteries

Lead-acid batteries are, between all types of batteries, the most used today as storage systems for photovoltaic applications. The sizing of the lead-acid batteries is based on some external parameters, solar irradiation and load consumption, and some battery characteristics, charge capacity and efficiency, depth of discharge, operating voltage, and ageing effects. The improvement of any of these parameters will result in an improvement of the sizing of the lead-acid battery and, consequently, of the sizing of the photovoltaic array. We have studied in this paper the influence of the improved capacity of lead-acid batteries with electrolyte circulation onto the sizing of the lead-acid battery and the PV array. The experimental results have shown that the lead-acid battery capacity can be improved as much as 20% if electrolyte circulation is used. The improvement results in a reduction of up to 30% in the size of the battery if combined with the improvement in the reduction of the battery capacity due to annual cycling and ageing, another beneficial effect of the electrolyte circulation. The reduction of size is extended to the PV array which is affected not only by the above mentioned effects, but also by the higher charge efficiency of the electrolyte circulation battery. The reduction in sizing the PV array can be as much as 41% for the most exigent operating conditions, deep depth of discharge and high discharge rate. The use of an electrolyte circulation system is especially useful in lead-acid batteries for PV systems which must operate at very deep cycling and require a minimum size of the battery block.     

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.     

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.     

Characterizing capacity loss of lithium oxygen batteries by impedance spectroscopy

Polymer based carbon aerogels were prepared by synthesis of a resorcinol formaldehyde gel followed by pyrolysis at 1073 K under Ar and activation of the resultant carbon under CO₂ at different temperatures. The prepared carbon aerogels were used as active materials in the preparation of cathode electrodes for lithium oxygen cells and the electrochemical performance of the cells was evaluated by galvanostatic charge/discharge cycling and electrochemical impedance measurements. It was shown that the storage capacity and discharge voltage of a Li/O₂ cell strongly depend on the porous structure of the carbon used in cathode. EIS results also showed that the shape and value of the resistance in the impedance spectrum of a Li/O₂ cell are strongly affected by the porosity of carbon used in the cathode. Porosity changes due to the build up of discharge products hinder the oxygen and lithium ion transfer into the electrode, resulting in a gradual increase in the cell impedance with cycling. The discharge capacity and cycle life of the battery decrease significantly as its internal resistance increases with charge/discharge cycling.     

Modeling of the capacity loss of a 12 V automotive lead-acid battery due to ageing and comparison with measurement data

One-dimensional modeling was carried-out to predict the capacity loss of a 12 V automotive lead-acid battery due to ageing. The model not only accounted for electrochemical kinetics and ionic mass transfer in a battery cell, but also considered the anodic corrosion of lead in sulfuric acid. In order to validate the modeling, modeling results were compared with the measurement data of the cycling behaviors of the lead-acid batteries having nominal capacity of 68 Ah that are mounted on the automobiles manufactured by Hyundai Motor Company. The cycling was performed under the protocol of the constant-current discharge and the constant-voltage charge. The discharge rate of C/3 was used. The range of state of charge was between 1 and 0.85. The voltage was kept constant at the gassing voltage until the charge current tapered to 10 mA. The retention capacity of the battery was measured with C/3 discharge rate before the beginning of cycling and after every 40 cycles of cycling. The modeling results were in good agreement with the measurement data.     

Electrical‐thermal behaviors of a cylindrical graphite‐NCA Li‐ion battery responding to external short circuit operation

Large amount of heat generated during an external short circuit (ESC) process may cause battery safety events. An experimental platform is established to explore the battery electrothermal characteristics during ESC faults. For 18650‐type nickel cobalt aluminum (NCA) batteries, ESC fault tests of different initial state of charge (SOC) values, different external resistances, or different ambient temperatures are carried out. The test case of a smaller external resistance is characterized by a shorter ESC duration with a faster cell temperature rise, whereas the case of a larger external resistance will last for a longer duration, discharge more electricity, and terminate in a slightly higher temperature. The tested batteries of high initial SOCs generally have higher temperature rise rates, smoother changes at the output current/voltage curves, but a smaller discharged capacity. The batteries of low initial SOCs can be overdischarged by the ESC operations. At low temperatures, say 0°C, the ESC process outputs much less electricity than the process at high temperatures, eg, 30°C. The initial low temperature has little effect on reducing the battery overheat due to ESC operations. The battery thermal behavior is of hysteresis property; analysis of heat generations reveals the subsequent increase of battery surface temperature after the completion of ESC discharge is due to the battery material abusive reaction heats. It is found from analytical and numerical analyses that there can have approximately 30°C temperature difference between the battery core and its surface during ESC operations. The interruption of ESC operation is very probably caused by the high battery core temperature, which leads to the destruction of solid‐electrolyte interface (SEI) film.     

磷酸铁锂电池内阻连续动态测量与分析

磷酸铁锂电池内阻测量目前大多存在耗时长、测量结果不连续等问题。文章提出一种新型的内阻测量方法——双倍率曲线法。基于该方法,对不同温度下电池内阻进行测量并进行误差分析。结合误差分析结果发现,该测量方法的适用放电状态（state of discharge, SoD）区间为5% ~ 90%。对该区间内平均内阻与温度之间的关系进行定量分析,得到平均内阻随温度变化的关系式。相比于以往的其他测量方法,该方法的提出能够有效缩短内阻测量时耗,可为在线内阻测量的实现提供一定的研究基础。     

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。     

锂离子电池电-热耦合模型分析及其温度场仿真研究

锂离子电池由于放电过程产生大量的热,不可避免的使得电池温度升高。研究大倍率放电时的电池温升,忽略电化学反应热,进一步简化原有的生热模型。为了得到电池温度分布,从电池内部结构出发,根据电流密度在集流板上的分布以及极耳处的收缩/扩散效应,分析集流板上电流密度的分布规律,从而建立电池的电-热耦合模型。通过生热模型模拟电池放电过程的温升现象,并与实验结果对比,发现模拟结果与实验结果能够很好地吻合。文章给出了电池在不同放电倍率条件下放电终了时的温度分布图,并解释了造成这种分布现象的原因。     

Illustration of experimental,machine learning,and characterization methods for study of performance of Li-ion batteries

The development of fault diagnosis of Li-ion batteries used in electric vehicles is vital. In this perspective, the present work conducted a comprehensive study for the evaluation of coupled and interactive influence of charging ratio, number of cycles, and voltage on the discharge capacity of Li-ion batteries to predict the life of battery. The charging-discharging experimental tests on Li-ion batteries have been performed. The data such as charging ratio, number of cycles, voltage, and discharge capacity of Li-ion batteries are measured. Machine learning approach of neural networks is then applied on the obtained data to compute the effects, normal distribution, parametric analysis, and sensitivity analysis of the input parameters on the capacity of battery. It can be noticed that discharge capacity increased with an increase in full voltage. Further, it has been observed from the sensitivity analysis that the full voltage is most relevant parameters to the capacity of the battery. Additionally, scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) of the electrodes before and after experiments have been performed, to investigate the elemental dissolution due to the charging/discharging cycles. The findings and analysis from the proposed study shall facilitate experts in making decisions on the remaining life and charging capacity of the battery.     

Modeling the discharge behavior of a lithium-sulfur battery

In lithium-sulfur (Li-S) batteries, the discharge performance depends greatly on a number of cell design parameters because of the complex reaction mechanisms in the cathode. Electrolyte-to-sulfur (E/S) ratio and carbon-to-sulfur (C/S) ratio in the cell are key examples of these critical design factors that define the Li-S battery performance. Here, a 1-D electrochemical model is reported to calculate the dependence of the discharge behavior of a Li-S battery on the E/S and C/S ratios. Proposed model describes the complex kinetics through two electrochemical and two dissolution/precipitation reactions. Concentration variations in the cathode are also taken into account in the model. Characteristic aspects of the discharge profile of a Li-S battery -the two distinct voltage plateaus and the voltage dip in between- are captured in the predicted voltage curve. Similar trends on the discharge performance of the Li-S cell with varying E/S and C/S ratios are projected; both voltage and discharge capacity of the Li-S battery are improved substantially with increasing C/S or E/S ratio up to a certain point, whereas, the dependence of the discharge performance on these factors is less substantial at higher ratios. This model offers a mechanistic interpretation of the influence of cell design on the Li-S battery performance.     

Current density and state of charge inhomogeneities in Li-ion battery cells with LiFePO4 as cathode material due to temperature gradients

Current density distributions and local state of charge (SoC) differences that are caused by temperature gradients inside actively cooled Li-ion battery cells are discussed and quantified. As an example, a cylindrical Li-ion cell with LiFePO₄ as cathode material (LiFePO₄-cell) is analyzed in detail both experimentally and by means of spatial electro-thermal co-simulations. The reason for current density inhomogeneities is found to be the local electrochemical impedance varying with temperature in different regions of the jelly roll. For the investigated cell, high power cycling and the resulting temperature gradient additionally cause SoC-gradients inside the jelly roll. The local SoCs inside one cell diverge firstly because of asymmetric current density distributions during charge and discharge inside the cell and secondly because of the temperature dependence of the local open circuit potential. Even after long relaxation periods, the SoC distribution in cycled LiFePO₄-cells remains inhomogeneous across the jelly roll as a result of hysteresis in the open circuit voltage. The occurring thermal electrical inhomogeneities are expected to influence local aging differences and thus, global cell aging. Additionally the occurrence of inhomogeneous current flow and SoC-development inside non-uniformly cooled battery packs of parallel connected LiFePO₄-cells is measured and discussed.