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.

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.

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%.

面向真实世界车辆LFP电池的深度学习SOC估计方法

电动汽车磷酸铁锂(LFP)电池的开路电压-荷电状态曲线在20%~95%荷电状态(SOC)范围内存在平台期,导致基于模型的方法难以准确估计SOC,而基于数据驱动的方法又存在真实世界准确的样本数据难以获取和实验环境无法完全模拟真实世界电池系统运行的问题。提出了一种面向真实世界车辆LFP电池的深度学习SOC估计方法,利用真实世界车辆LFP电池系统运行数据通过反向安时积分法为其自动标签准确的SOC,构建了CNNGRUM新模型预测SOC的方法,通过多层卷积神经网络结合多层门控循环单元,基于电流、电压、温度和充电过程安时量四个特征实现对LFP电池SOC的估计。通过在真实世界的20辆电动汽车LFP电池上进行模型训练和验证,实现了最大绝对误差为2.85%、均方根误差(RMSE)为0.61%、平均绝对误差(MAE)为0.42%的SOC准确估计。

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.

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.

LFP电池热失控液氮冷却惰化理论分析方法研究

传统的商用灭火剂扑救锂离子电池热失控火灾和抑制复燃的效果不佳,液氮作为一种高效的灭火剂,其冷却抑制锂离子电池热失控的效果得到了很多研究机构试验验证,但目前针对液氮灭火用量和灭火效能尚缺乏理论分析方法。笔者通过对液氮灭火机理的理论分析,研究确定了液氮冷却和惰化理论分析计算方法。方法中通过试验和理论分析确定热失控放热热量、液氮吸热热量、液氮惰化用量等,并通过实尺试验验证方法的有效性。以280 Ah磷酸铁锂电池热失控为例,依据理论分析方法,计算得到了惰化抑爆和冷却的最低液氮用量,在有效容积为38.88 m3的爆炸试验箱体内,施加了83.39 kg液氮后,24 h间隔点火48次,均未出现燃爆现象。通过实际案例验证理论分析方法的有效性和合理性,提出的理论分析方法为液氮灭火抑爆的设计和有效性分析提供评价手段和方法,进一步增强磷酸铁锂电池舱式储能系统的安全性。

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.

磷酸铁锂离子电池热失控产物爆炸下限预测方法

为准确预测磷酸铁锂电池热失控产物的爆炸下限,在密闭压力容器内开展了磷酸铁锂电池热失控实验,结合热失控特性和气相色谱-质谱联用技术,计算了热失控产物气体组分,基于能量守恒方程和绝热火焰温度,建立了磷酸铁锂电池热失控产物爆炸下限的预测模型,并验证了绝热火焰温度法、Le Chatelier法和Jones法的准确性,考察了电解液蒸气对热失控产物爆炸下限的影响。结果表明,常温下采用Le Chatelier法计算得到的爆炸下限偏差最小,为1.14%;采用绝热火焰温度法计算结果偏差最大,为10.02%。在60%~100%荷电状态(state of charge, SOC)范围内,磷酸铁锂电池热失控气体的爆炸下限先升后降。当热失控产物考虑电解液蒸气时,60%SOC磷酸铁锂电池热失控产物爆炸下限仅为3.93%,较未考虑电解液蒸气热失控气体的爆炸下限降低了22.49%,这说明电解液蒸气提高了磷酸铁锂电池热失控产物的爆炸风险。

磷酸铁锂储能预制舱火灾烟气扩散及温度变化规律

随着电化学储能的大规模应用,储能预制舱安全问题日益突出。对储能预制舱内不同热失控位置下的储能预制舱火灾差异进行研究,可以帮助设计更有效的监测和灭火系统,提升储能预制舱安全性能。因此,模拟研究不同热失控位置下储能预制舱火灾烟气扩散及温度变化规律具有重要意义。文中基于直接数值模拟和大涡模拟方法,依据实际储能预制舱尺寸构建磷酸铁锂储能预制舱的数值模型,引入更符合火情发展的t2模型,通过模拟不同热失控位置的火灾情境,研究储能预制舱内烟气扩散和温度变化规律。仿真结果表明,热失控的位置不同,烟气具有不同的动态行为,热失控位置越靠近底层,烟气运动越快,充满储能预制舱时间越短。当热失控位置靠近舱顶,在高度1.85 m以上的区域温度较高,并伴随显著的温度波动时,储能预制舱水平方向上的温度差显著增大。文中进一步分析额定容量为1.2 MW·h的标准储能预制舱的灭火系统设计方案,发现全氟己酮灭火系统在喷淋强度为20 L/(min·m2)、喷淋角度为120°、全氟己酮灭火剂粒径大小为50μm时,能有效控制火灾,减少火灾造成的损害。文中的研究成果可为储能预制舱内监测预警装置分布式布署策略及消防安全设计提供理论指导。

正极补锂剂LFO对磷酸铁锂电池的性能影响

在正极中加入少量(3%)富锂铁酸锂(Li5FeO4,LFO)补锂剂,制备了一款补锂的大容量磷酸铁锂电池。补锂剂克容量约为680 mAh/g,有效地补充了首次充电的锂损失。对补锂前后极片的形貌,电池的内阻、低温放电、倍率充放电和循环性能进行了对比测试。结果表明补锂前后的极片形貌几乎无差别,补锂剂提供的富裕的锂离子显著降低了电荷转移阻抗,电池直流内阻下降,使得电池的低温放电和倍率充放电性能明显改善。补锂剂对电池循环性能的改善尤为显著,未补锂电池循环1224次,剩余容量是初始容量的94.68%;补锂后电池循环1224次后,仍有初始容量的100.28%,且容量下降的趋势也更为平缓。

磷酸铁锂电芯充放电特性研究与探讨

以105 A·h方形铝壳磷酸铁锂(简称LFP)电池单体为对象,研究了磷酸铁锂电池单体在不同荷电状态(简称So C)下温度对开路电压(简称OCV)的影响系数,温度对LFP电池单体放电容量的影响,放电倍率对放电容量的影响,以及温度和荷电状态对高倍率长脉冲放电测试性能的影响。SoC在30%以下,温度对OCV的影响系数为负值,而SoC在30%以上,温度对OCV影响不显著。随着温度的降低,LFP电池单体的放电容量逐渐降低。随着放电倍率的增加,放电容量逐渐降低。当温度低于0℃以下时,LFP电池单体的高倍率放电性能明显降低,且在相同SoC下,温度对低温高倍率放电影响不再呈线性规律。

LFP/C掺杂型PVDF-HFP隔膜及其电化学性能研究

本论文向聚偏氟乙烯-六氟丙烯中添加磷酸铁锂纳米颗粒制备得到PVDF-HFP/LFP复合隔膜材料。通过这种掺杂改性,提升了隔膜的吸液率,湿润性,热稳定性,以此提升电池的放电比容量和循环性能。电池正极使用经过碳包覆的磷酸铁锂材料,负极使用金属锂片,通过制备的不同隔膜组装电池探究磷酸铁锂纳米颗粒的添加对PVDF-HFP隔膜性能的影响,并研究了不同比例的磷酸铁锂纳米颗粒对聚合物隔膜的影响。

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.

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.

过充电触发的LFP和NCM锂离子电池的热失控行为:差异与原因

软包锂离子电池相比较于硬壳电池具有更高的能量密度,由于特殊的电池结构软包锂离子电池具备特殊的热失控行为和规律。本工作研究了以磷酸铁锂(LFP)和镍钴锰酸锂(NCM)材料为正极的两种软包锂离子电池在不同的倍率(0.5~3 C)电流下过充电后的失效和热失控行为,分析了电池的质量损失、失效电压、电池温升方面的差异。结果表明,LFP和NCM电池在过充电后均会因发生副反应生成气体导致铝塑膜外壳破裂,1 C倍率电流下LFP电池在充电至133.4%带电状态(SOC)时发生破裂,并导致电池失效,而NCM电池在充电至143.8%SOC时破裂,随后诱发热失控和着火。电池破裂电压均随充电倍率的增加(0.5~3 C)而呈现先增大后减小的趋势,在1.5 C时破裂电压最高,LFP电池的破裂电压高于NCM电池。此外,LFP和NCM电池的质量损失范围分别为2.07%~5.82%和28.51%~36.75%,随充电倍率变化不明显。研究还揭示了LFP和NCM电池过充电过程中温度升高的不同阶段特征,并从材料分子结构的角度对该差异的原因进行了分析。研究结果可为新能源汽车用锂电池单体选型提供参考。

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）.

Synthesis and characterization of LiFePO_4/C composite used as lithium storage electrodes

LiFePO4/C composites with good rate capability and high energy density were prepared by adding sugar to the synthetic precursor. A significant improvement in electrode performance was achieved. The resulting carbon contents in the sample 1 and sample 2 are 3.06% and 4.95%（mass fraction）, respectively. It is believed that the synthesis of LiFePO4 with sugar added before heating is a good method because the synthesized particles having uniform small size are covered by carbon. The performance of the cathodes was evaluated using coin cells. The samples were characterized by X-ray diffraction and scanning electron microscope observation. The addition of carbon limits the particles size growth and enables high electron conductivity. The LiFePO4/C composites show very good electrochemical performance delivering about 142 mAh/g specific capacity when being cycled at the C/10 rate. The capacity fade upon cycling is very small.

Theoretical model of lithium iron phosphate power battery under high-rate discharging for electromagnetic launch

Due to the large error of the traditional battery theoretical model during large-rate discharge for electromagnetic launch,the Shepherd derivative model considering the factors of the pulse cycle condition,temperature,and life is proposed by the Naval University of Engineering.The discharge rate of traditional lithium-ion batteries does not exceed 10C,while that for electromagnetic launch reaches 60C.The continuous pulse cycle condition of ultra-large discharging rate causes many unique electrochemical reactions inside the cells.The traditional model cannot accurately describe the discharge characteristics of the battery.The accurate battery theoretical model is an important basis for system efficiency calculation,precise discharge control,and remaining capacity prediction.To this purpose,an experimental platform for electromagnetic launch is built,and discharge characteristics of the battery under different rate,temperature,and life decay are measured.Through the experimental test and analysis,the reason that the traditional model cannot accurately characterize the large-rate discharge process is analyzed.And a novel battery theoretical model is designed with the help of genetic algorithm,which is integrated with the electromagnetic launch topology.Numerical simulation is compared with the experimental results,which verifies the modeling accuracy for the large-rate discharge.On this basis,a variety of discharge conditions are applied to test the applicability of the model,resulting in better results.Finally,with the continuous cycle-pulse condition in the electromagnetic launch system,the stability and accuracy of the model are confirmed.