Effect of safety valve types on the gas venting behavior and thermal runaway hazard severity of large-format prismatic lithium iron phosphate batteries

The safety valve is an important component to ensure the safe operation of lithium-ion batteries(LIBs).However,the effect of safety valve type on the thermal runaway(TR)and gas venting behavior of LIBs,as well as the TR hazard severity of LIBs,are not known.In this paper,the TR and gas venting behavior of three 100 A h lithium iron phosphate(LFP)batteries with different safety valves are investigated under overheating.Compared to previous studies,the main contribution of this work is in studying and evaluating the effect of gas venting behavior and TR hazard severity of LFP batteries with three safety valve types.Two significant results are obtained:(Ⅰ)the safety valve type dominates over gas venting pressure of battery during safety venting,the maximum gas venting pressure of LFP batteries with a round safety valve is 3320 Pa,which is one order of magnitude higher than other batteries with oval or cavity safety valve;(Ⅱ)the LFP battery with oval safety valve has the lowest TR hazard as shown by the TR hazard assessment model based on gray-fuzzy analytic hierarchy process.This study reveals the effect of safety valve type on TR and gas venting,providing a clear direction for the safety valve design.

Study on Preparation of Cathode Material of Lithium Iron Phosphate Battery by Self-Craning Thermal Method

The cathode material of carbon-coated lithium iron phosphate(LiFePO4/C)lithium-ion battery was synthesized by a self-winding thermal method.The material was characterized by X-ray diffraction(XRD)and scanning electron microscope(SEM).The electrochemical properties of LiFePO4/C materials were measured by the constant current charge-discharge method and cyclic voltammetry.The results showed that the LiFePO4/C material prepared by the self-propagating heat method has a typical olivine crystal structure,and the product had fine grains and good electrochemical properties.The optimal sintering temperature is 700℃,the sintering time is 24 h,the particle size of the lithium iron phosphate material is about 300 nm,and the maximum discharge capacity is 121 mAh/g at 0.1 C rate.

Process for recycle of spent lithium iron phosphate battery via a selective leaching-precipitation method

Applying spent lithium iron phosphate battery as raw material,valuable metals in spent lithium ion battery were effectively recovered through separation of active material,selective leaching,and stepwise chemical precipitation.Using stoichiometric Na2S2O8 as an oxidant and adding low-concentration H2SO4 as a leaching agent was proposed.This route was totally different from the conventional methods of dissolving all of the elements into solution by using excess mineral acid.When experiments were done under optimal conditions(Na2S2O8-to-Li molar ratio 0.45,0.30 mol/L H2SO4,60℃,1.5 h),leaching efficiencies of 97.53% for Li^+,1.39%for Fe^3+,and 2.58% for PO4^3−were recorded.FePO4 was then recovered by a precipitation method from the leachate while maintaining the pH at 2.0.The mother liquor was concentrated and maintained at a temperature of approximately 100℃,and then a saturated sodium carbonate solution was added to precipitate Li2CO3.The lithium recovery yield was close to 80%.

Hydrometallurgical recovery of lithium carbonate and iron phosphate from blended cathode materials of spent lithium-ion battery

The recycling of cathode materials from spent lithium-ion battery has attracted extensive attention,but few research have focused on spent blended cathode materials.In reality,the blended materials of lithium iron phosphate and ternary are widely used in electric vehicles,so it is critical to design an effective recycling technique.In this study,an efficient method for recovering Li and Fe from the blended cathode materials of spent LiFePO_(4)and LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)batteries is proposed.First,87%A1 was removed by alkali leaching.Then,91.65%Li,72.08%Ni,64.6%Co and 71.66%Mn were further separated by selective leaching with H_(2)SO_(4)and H_(2)O_(2).Li,Ni,Co and Mn in solution were recovered in the form of Li_(2)CO_(3)and hydroxide respectively.Subsequently,98.38%Fe was leached from the residue by two stage process,and it is recovered as FePO_(4)·2H_(2)O with a purity of 99.5%by precipitation.Fe and P were present in FePO_(4)·2H_(2)O in amounts of 28.34%and 15.98%,respectively.Additionally,the drift and control of various components were discussed,and cost-benefit analysis was used to assess the feasibility of potential application.

Accurate Modeling of Prismatic Type High Current Lithium-Iron-Phosophate (LiFePO4) Battery for Automotive Applications

With accurate battery modeling, circuit designers and automotive control algorithms developers can predict and optimize the battery performance. In this paper, an experimental verification of an accurate model for prismatic high current lithium-iron-phosphate battery is presented. An automotive TSLFP160AHA lithium-iron-phosphate battery bank is tested. The different capacity GBDLFMP60AH battery bank is used to validate the model extracted from the former battery. Effect of current, stacking and SOC upon the battery parameters performance is investigated. Six empirical equations are obtained to extract the prismatic type LiFePO4 model as a function of SOC. Based on comparing the measured and simulated data, a well accuracy of less than 50mV maximum error voltage with 1.7% operating time error referred to the measured data is achieved. The model can be easily modified to simulate different batteries and can be extended for wide ranges of different currents.

Recovery and regeneration of LiFePO_(4)from spent lithium-ion batteries via a novel pretreatment process

The recycling of spent LiFePO_(4)batteries has received extensive attention due to its environmental impact and economic benefit.In the pretreatment process of spent LiFePO_(4)batteries,the separation of active materials and current collectors determines the difficulty of the re-covery process and product quality.In this work,a facile and efficient pretreatment process is first proposed.After only freezing the electrode pieces and immersing them in boiling water,LiFePO_(4)materials were peeled from the Al foil.Then,after roasting under an inert atmosphere and sieving,all the cathode and anode active materials were easily and efficiently separated from the Al and Cu foils.The active materials were subjected to acid leaching,and the leaching solution was further used to prepare FePO_(4)and Li_(2)CO_(3).Finally,the battery-grade FePO_(4)and Li_(2)CO_(3)were used to re-synthesize LiFePO_(4)/C via the carbon thermal reduction method.The discharge capacities of re-synthesized LiFePO_(4)/C cathode were 144.2,139.0,133.2,125.5,and 110.5 mA·h·g−1 at rates of 0.1,0.5,1,2,and 5 C,which satisfies the requirement for middle-end LiFePO_(4)batteries.The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.

Composites of Graphene and LiFePO_4 as Cathode Materials for Lithium-Ion Battery:A Mini-review

This mini-review highlights selectively the recent research progress in the composites of Li Fe PO4 and graphene. In particularly, the different fabrication protocols, and the electrochemical performance of the composites are summarized in detail. The structural and morphology characters of graphene sheets that may affect the property of the composites are discussed briefly. The possible ongoing researches in area are speculated upon.

Surfactant assisted solvothermal synthesis of LiFePO4 nanorods for lithium-ion batteries

Well-shaped and uniformly dispersed LiFePOnanorods with a length of 400–500 nm and a diameter of about 100 nm, are obtained with participation of a proper amount of anion surfactant sodium dodecyl sulfonate（SDS） without any further heating as a post-treatment. The surfactant acts as a self-assembling supermolecular template, which stimulated the crystallization of LiFePOand directed the nanoparticles growing into nanorods between bilayers of surfactant（BOS）. LiFePOnanorods with the reducing crystal size along the b axis shorten the diffusion distance of Liextraction/insertion, and thus improve the electrochemical properties of LiFePOnanorods. Such prepared LiFePOnanorods exhibited excellent specific capacity and high rate capability with discharge capacity of 151 mAh/g, 122 mAh/g and 95 mAh/g at 0.1C, 1 C and 5 C, respectively. Such excellent performance of LiFePOnanorods is supposed to be ascribed to the fast Lidiffusion velocity from reduced crystal size along the b axis and the well electrochemical conductivity. The structure, morphology and electrochemical performance of the samples were characterized by XRD, FE-SEM, HRTEM, charge/discharge tests, and EIS（electrochemical impedance spectra）.

液氮抑制32650型磷酸铁锂电池组热失控传播特性试验研究

文章从磷酸铁锂电池组热失控危险特性出发,通过试验研究32650型磷酸铁锂电池单体热失控特征及其电池组间热失控传播过程。探究利用液氮喷淋阻断电池组间热失控传播,分析液氮对磷酸铁锂电池的防灭火效能。结果表明:单体锂电池热失控可划分为被动加热、安全阀泄压、自反应、喷射火、明火熄灭等5个阶段,单体电池温度变化曲线呈倒“V”形。液氮可有效阻断电池组间的热失控传播,能够大幅降低喷射火阶段的电池峰值温度。且喷淋时间越长,阻止电池组热失控传播越明显。30 s液氮喷淋条件下,除电池A1外,其他电池未进入安全阀泄压阶段。

基于电热耦合模型的宽温域锂离子电池SOC/SOP联合估计

准确的状态估计对于锂离子电池安全可靠运行具有重要意义,但由于非线性强,多参数耦合,实现宽温域多参数联合在线估计难度较大。考虑到温度影响,建立电热耦合模型,采用扩展卡尔曼滤波算法(EKF)在线辨识电池参数,通过电压及温度仿真验证了模型的准确性;然后针对无迹卡尔曼滤波算法(UKF)历史数据利用率低的问题,引入多新息理论(MI)改进UKF,改进后的算法在非电压平台区荷电状态(SOC)估计均方根误差不超过1.2%,相较于改进前误差降低了30%以上,并结合安时积分法设计切换算法,解决了MIUKF算法在磷酸铁锂电池电压平台区无法通过电压反馈修正SOC估计误差的问题,实现了宽温域复杂工况下全区间SOC的准确估计,在不同SOC初始值条件下验证了结合算法的准确性,均方根误差不超过3%,为峰值功率(SOP)估计提供了可靠的SOC值;最后将温度约束引入到SOP估计中,提出多约束条件下的SOP估计方法,结果表明在高温条件下,温度起到关键限制作用,可以防止电池温升过大,减少安全隐患。

从废旧电池中回收二水磷酸铁再生LiFePO_(4)/C

使用酸浸—加热回流法从废旧磷酸铁锂电池中回收得到二水磷酸铁,将其作为原料并添加一定量的锂源和碳源,通过高温固相法再生了LiFePO_(4)/C,并研究了温度对再生LiFePO_(4)/C电化学性能的影响。首先采用酸浸—加热回流法对废旧磷酸铁锂正极片进行处理生成FePO_(4)·2H_(2)O,洗涤烘干后研磨得到FePO_(4)·2H_(2)O粉末,XRD表征和ICP测试结果显示回收得到的FePO_(4)·2H_(2)O结构完整、纯度较高。然后在FePO_(4)·2H_(2)O粉末中添加碳源,在高温下制备LiFePO_(4)/C材料,对其进行结构与形貌表征以及电化学测试,发现以葡萄糖为碳源、温度为700℃、葡萄糖量为理论生成磷酸铁锂质量的17%时再生的LiFePO_(4)/C电化学性能最佳,0.3 C倍率下再生的LiFePO_(4)/C首周放电比容量可达141.8 mAh/g,循环100周后容量保持率可维持在94.3%。通过与商用LiFePO_(4)/C进行电化学性能对比,进一步验证了该工艺再生的LiFePO_(4)/C有着优良的电化学性能。

基于集成聚类的退役锂电池直接分组

针对退役电池筛选分组效率低的问题,提出了一种基于加权表决集成聚类算法的退役锂离子电池直接分组方法。提取充电电压片段特征,对特征进行降维,并使用集成聚类算法直接对特征进行分组,实现退役锂离子电池分组。该方法只需要得到部分恒流充电曲线便可实现退役锂离子电池的按容量分组,提高了筛选效率。搭建了磷酸铁锂电池仿真和实验平台,对所提的电池筛选、分组策略进行仿真和实验分析。从退役电池分组容量精度和分组效率的角度验证了所提策略的正确性和有效性。

退役磷酸铁锂电池负极石墨的预锂化再生

对退役磷酸铁锂(LiFePO_(4))电池的负极石墨进行预锂化,使石墨变为锂碳化合物并进行热处理,从而实现石墨的晶型转变.将预锂化后的LiFePO_(4)电池热处理,回收得到的石墨经不同处理,所得样品分别与导电炭黑和黏结剂等物质进行混合制成新的电极,组装成电池后进行电池的性能测试.结果表明,在电流为0.1C的条件下,预锂化热处理的石墨样品经酸浸后所制成的纽扣电池平均放电比容量为322.3 mAh·g^(-1),远远高于其他对比组,其循环稳定性也强于人造石墨.说明退役电池负极石墨通过预锂化、热处理和酸浸处理后能够得到优质再生石墨.

优先提锂湿法工艺回收废旧磷酸铁锂电池

文章详细介绍了一种优先提锂湿法回收碳酸锂的工艺流程,先用碱除铝,再酸浸分离磷酸铁,除杂后沉锂,工艺流程简化、试剂消耗量小、锂浸出选择性较高,工艺经济效益相对更好,可以为磷酸铁锂电池回收企业提供一种工艺流程简化、试剂消耗量小、锂浸出选择性较高、工艺经济效益相对更好的工艺技术路线。

Recursive calibration for a lithium iron phosphate battery for electric vehicles using extended Kalman filtering

In this paper,an efficient model structure composed of a second-order resistance-capacitance network and a simply analytical open circuit voltage versus state of charge(SOC) map is applied to characterize the voltage behavior of a lithium iron phosphate battery for electric vehicles(EVs).As a result,the overpotentials of the battery can be depicted using a second-order circuit network and the model parameterization can be realized under any battery loading profile,without a special characterization experiment.In order to ensure good robustness,extended Kalman filtering is adopted to recursively implement the calibration process.The linearization involved in the calibration algorithm is realized through recurrent derivatives in a recursive form.Validation results show that the recursively calibrated battery model can accurately delineate the battery voltage behavior under two different transient power operating conditions.A comparison with a first-order model indicates that the recursively calibrated second-order model has a comparable accuracy in a major part of the battery SOC range and a better performance when the SOC is relatively low.

高温固相修复再生磷酸铁锂正极材料研究进展

磷酸铁锂电池作为广泛应用的锂离子电池之一,其关键电极材料的高效回收循环利用在资源、环境、经济等方面具有重要的战略意义。高温固相修复技术能够实现磷酸铁锂正极材料短流程、低成本、高效率、绿色环保的循环利用,获得了广泛的关注和研究。针对高温固相修复再生磷酸铁锂正极材料,介绍了此类材料的电化学性能失效机理,从锂补充、缺陷修复和强化锂的迁移等方面对磷酸铁锂正极材料的修复机理进行了分析;阐述了焙烧温度、保温时间、补锂量等修复再生工艺参数对高温固相法修复磷酸铁锂正极材料的影响;分析了表面包覆和离子掺杂对提升磷酸铁锂正极材料电化学性能的影响和机理;并对高温固相修复法修复磷酸铁锂正极材料的可控制备、杂质控制和材料改性等方面的未来前景进行了展望。

退役磷酸铁锂电池梯次利用生命周期评价与碳减排情景分析

以磷酸铁锂电池为研究对象,综合考虑梯次利用比例、使用周期及电池容量等因素,设定不同梯次利用场景,采用生命周期评价方法量化退役动力电池在梯次利用及后续报废处置阶段的环境影响,并对不同梯次利用率情景下的碳减排量进行分析.结果表明,与直接再生利用相比,储能、通信基站、低速电源三种梯次利用场景均表现为环境效益.其中,储能场景环境效益最大,其在气候变化、化石能源消耗、人体毒性-非致癌、陆地生态毒性指标等环境影响指标上均表现出相对优势.基于电池退役量和梯次利用去向,进一步计算出2023年全年磷酸铁锂电池梯次利用的碳减排量为1.05×10^(8) kg CO_(2)eq.当梯次利用率保持当前水平或以10%增长时,至2030年其全年碳减排量可达1.55×10^(9)kg CO_(2)eq.和5.98×10^(9)kg CO_(2)eq.,梯次利用具有良好的减污降碳环境表现.

面向实车应用的磷酸铁锂电池容量辨识及特异性优化方法研究

锂离子电池作为电动汽车的重要部件之一,其健康程度直接影响车辆的续航能力、安全性能以及整体运行效率。其中,容量作为描述电池健康状态的重要指标,实车条件下的准确估计是一个难题。为此,本文提出一种结合安时积分与等效电路模型,将容量作为待辨识参数之一,通过粒子群优化算法以实现容量辨识的方法。在此基础上,聚焦于磷酸铁锂电池的电压特殊性,提出了一种面向慢充工况的特异性优化方法,以解决容量辨识过程中模型端电压拟合较差的问题,主要通过截取充电末期电压片段与使用双维度目标函数两种方法实现。本文基于两款搭载磷酸铁锂电池的电动汽车车型进行了精度验证。鉴于实车数据缺乏容量标签,本文首先基于静置充电片段计算容量作为标签值。由于标签数量不足,又采用小里程下的标称容量作为标签,通过这两种方法进行精度验证。结果显示,两款车型的平均绝对百分比误差分别为2.33%和3.38%,表明该方法具有较高的精度与适用性,为实车容量估计提供了一种思路与方法。

气凝胶灭火剂抑制锂离子储能电池热失控特性研究

通过对比试验探究了气凝胶灭火剂对锂离子储能电池热失控的抑制效果。研究满荷电状态下的100 Ah磷酸铁锂储能电池热失控演变过程特征参数,识别出3个灾害演变特征拐点作为灭火剂施加的指导节点。在相同节点分别施加灭火参数一致的气凝胶灭火剂与细水雾开展灭火对比测试。结果表明:触发明火前施加灭火剂均可有效阻断电池内部放热副反应,两者表现出相似的冷却效能;电池起火后,气凝胶灭火剂展现出更为出色的明火抑制效果,其接触电池表面形成的致密泡沫可有效阻隔氧气,实现快速灭火;对于已经触发热失控的情形,气凝胶灭火剂凭借预热覆盖效果,显著缩短电池射流火持续时间,可大幅降低电池火灾危害。