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%.

PEG-combined liquid phase synthesis and electrochemical properties of carbon-coated Li_3V_2(PO_4)_3

The carbon-coated monoclinic Li3V2(PO4)3(LVP) cathode materials were successfully synthesized by liquid phase method using PEG as reducing agent and carbon source. The effects of relative molecular mass of PEG on the properties of Li3V2(PO4)3/C were evaluated by X-ray diffraction(XRD), scanning electron microscope(SEM) and electrochemical performance tests. The SEM images show that smaller size particles are obtained by adding larger and smaller PEGs. The electrochemical cycling of Li3V2(PO4)3/C prepared by both PEG200 and PEG20 k has a high initial discharge capacity of 131.1 mA·h/g at 0.1C during 3.0-4.2 V, and delivers a reversible discharge capacity of 123.6 m A·h/g over 30 cycles, which is better than that of other samples. The improvement in electrochemical performance is caused by its improved lithium ion diffusion coefficient for the macroporous morphology, which is verified by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS).

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.

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.

Effects of different iron sources on the performance of LiFePO_4/C composite cathode materials

Olivine LiFePO4/C composite cathode materials were synthesized by a solid state method in N2 ＋ 5vol% H2 atmosphere. The effects of different iron sources, including Fe（OH）3 and FeC2O4·2H2O, on the performance of as-synthesized cathode materials were investigated and the causes were also analyzed. The crystal structure, the morphology, and the electrochemical performance of the prepared samples were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, laser particle-size distribution measurement, and other electrochemical techniques. The results demonstrate that the LiFePO4/C materials obtained from Fe（OH）3 at 800℃ and FeC2O4·2H2O at 700℃ have the similar electrochemical performances. The initial discharge capacities of LiFePO4/C synthesized from Fe（OH）3 and FeC2O4·2H2O are 134.5 mAh.g^-1 and 137.4 mAh.g^-1 at the C/5 rate, respectively. How- ever, the tap density of the LiFePO4/C materials obtained from Fe（OH）3 are higher, which is significant for the improvement of the capacity of the battery.

Perspective on cycling stability of lithium-iron manganese phosphate for lithium-ion batteries

Lithium-iron manganese phosphates(LiFex Mn_(1-x)PO_(4),0.1<x<0.9)have the merits of high safety and high working voltage.However,they also face the challenges of insufficient conductivity and poor cycling stability.Some progress has been achieved to solve these problems.Herein,we firstly summarized the influence of different electrolyte systems on the electrochemical performance of LiFexMn_(1-x)PO_(4),and then discussed the effect of element doping,lastly studied the influences of conductive layer coating and morphology control on the cycling stability.Finally,the prospects and challenges of developing high-cycling LiFexMn_(1-x)PO_(4) were proposed.

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.

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.

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.

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.

3D amorphous carbon and graphene co-modified LiFePO_4 composite derived from polyol process as electrode for high power lithium-ion batteries

Amorphous carbon and graphene co-modified LiFePO4 nanocomposite has been synthesized via a facile polyol process in connection with a following thermal treatment.Various characterization techniques,including XRD.Mossbauer spectra,Raman spectra,SEM,TEM,BET,O2-TPO,galvano charge-discharge,CV and EIS were applied to investigate the phase composition,carbon content,morphological structure and electrochemical performance of the synthesized samples.The effect of introducing way of carbon sources on the properties and performance of LiFePO4/C/graphene composite was paid special attention.Under optimized synthetic conditions,highly crystalized olivine-type LiFePO4was successfully obtained with electron conductive Fe2P and FeP as the main impurity phases.SEM and TEM analyses demonstrated the graphene sheets were randomly distributed inside the sample to create an open structured LiFePO4 with respect to graphene,while the glucosederived carbon mainly coated over LiFeP04 particles which effectively connected the graphene sheets and LiFePO4 particles to result in a more efficient charge transfer process.As a result,favorable electrochemical performance was achieved.The performance of the amorphous carbon-graphene co-modified LiFePO4 was further progressively improved upon cycling in the first 200 cycles to reach a reversible specificcapacity as high as 97 mAh·g-1 at 10 C rate.

Highly selective and green recovery of lithium ions from lithium iron phosphate powders with ozone

Since lithium iron phosphate cathode material does not contain high-value metals other than lithium,it is therefore necessary to strike a balance between recovery efficiency and economic benefits in the recycling of waste lithium iron phosphate cathode materials.Here,we describe a selective recovery process that can achieve economically efficient recovery and an acceptable lithium leaching yield.Adjusting the acid concentration and amount of oxidant enables selective recovery of lithium ions.Iron is retained in the leaching residue as iron phosphate,which is easy to recycle.The effects of factors such as acid concentration,acid dosage,amount of oxidant,and reaction temperature on the leaching of lithium and iron are comprehensively explored,and the mechanism of selective leaching is clarified.This process greatly reduces the cost of processing equipment and chemicals.This increases the potential industrial use of this process and enables the green and efficient recycling of waste lithium iron phosphate cathode materials in the future.

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.

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。

失效锂萃取剂中Fe(Ⅲ)的回收及制备电池级磷酸铁的工艺研究

盐湖卤水萃取法提锂的工艺中,磷酸三丁酯-FeCl_(3)-煤油协萃体系在多次循环使用后萃取能力会下降甚至失效。将失效锂萃取剂中的Fe(Ⅲ)回收利用对盐湖提锂行业的持续发展具有重要意义。在高浓度盐酸体系中模拟失效锂萃取剂,以其中的Fe(Ⅲ)为铁源,NH_(4)H_(2)PO_(4)溶液为磷源,在非均相体系中制备电池级磷酸铁。研究了反应时间、氨水加入量、NH_(4)H_(2)PO_(4)溶液浓度、反应温度和搅拌速率对产品产率、粒径(D_(50))和铁磷物质的量比的影响。结果表明,在优化的工艺条件下,可制得高纯度的单斜晶系二水磷酸铁,产率为89.43%、铁磷物质的量比为0.98、D_(50)为1.81μm、比表面积为37.38 m^(2)/g、含水量为19.64%,符合电池级磷酸铁的行业标准。以自制的磷酸铁为前驱体制备的Li Fe PO_(4)/C性能良好,在0.1C倍率下的首次放电比容量为146.58 m A·h/g,首次充放电效率为94.90%,恒流充放电循环80圈后的容量保持率为91.72%。研究表明,采用NH_(4)H_(2)PO_(4)溶液反萃沉淀法可有效回收失效锂萃取剂中的Fe(Ⅲ)并制备出电池级磷酸铁。

基于铁锈红和废锂箔制备LiFePO_(4)/C正极材料的储锂性能

磷酸铁锂电池的需求大、市场垄断而导致原材料价格日益高涨。以铁锈红和废锂箔为原材料,采用磷酸铁工艺制备了LiFePO_(4)/C粉末,并测试其电化学储锂性能。结果表明:LiFePO_(4)/C粉末由粒径尺寸为110~400nm的颗粒组成,在1.0C循环350圈后的可逆比容量和容量保持率分别为129.7mAh/g和98.0%,与商业LiFePO_(4)正极材料性能相当。可见,该结果降低了LiFePO 4的制备成本,有利于循环经济和可持续发展。