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%.

Mixed salts for lithium iron phosphate-based batteries operated at wide temperature range

To achieve good performance for LiFePO4-based batteries operated at a wide temperature range,mixed salts of LiBF4 LiBOB（lithium bis（oxalato）borate） and LiTFSI（lithium bis（trifluoromethanesulfonyl）imide）-LiBOB were investigated as alternative lithium salts to LiPF6 in non-aqueous electrolytes.LiFePO4/Li half cells using LiPF6,LiBF4-LiBOB and LiTFSI-LiBOB slats as lithium salts were investigated by galvanostatic cycling,cyclic voltammetry,thermogravimetric analysis.The results show that LiBF4-LiBOB and LiTFSI-LiBOB mixed salts are much more thermally stable than LiPF6.Corrosion of Al foil in the LiTFSI-based electrolytes can be suppressed successfully by the addition of LiBOB as a co-salt.The electrochemical performance of LiBF4-LiBOB and LiTFSI-LiBOB mixed salts based cells are both better than that of LiPF6-based cell.LiTFSI-LiBOB mixed salt based electrolyte is considered to be a very promising electrolyte candidate for Li-ion batteries that will be used in wide-temperature applications.

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.

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.

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.

Nanocomposite LiFePO_4·Li_3V_2(PO_4)_3/C synthesized by freeze-drying assisted sol-gel method and its magnetic and electrochemical properties

Nano-sized LiFePO_4·Li_3V_2（PO_4）_3/C was synthesized via a sol-gel route combining with freeze-drying. X-ray diffraction results show that this composite mainly consists of olivine Li Fe PO4 and monoclinic Li3 V2（PO4）3 phases with small amounts of V-doped LiFePO_4 and Fe-doped Li_3V_2（PO_4）_3. The magnetic properties of LiFePO_4·Li_3V_2（PO_4）_3/C are significantly different from LiFePO_4/C. Trace quantities of ferromagnetic impurities and Fe_2P are verified in LiFePO_4/C and LiFePO_4·Li_3V_2（PO_4）_3/C by magnetic tests, respectively. LiFePO_4·Li_3 V_2（PO_4）_3/C possesses relatively better rate capacities and cyclic stabilities, especially at high charge-discharge rates.The initial discharge capacities are 136.4 and 130.0 mA h g^（-1）,and the capacity retentions are more than 98% after 100 cycles at 2C and 5C, respectively, remarkably better than those of LiFePO_4/C. The excellent electrochemical performances are ascribed to the mutual doping of V^（3＋）and Fe^（2＋）, complementary advantages of LiFePO_4 and Li_3V_2（PO_4）_3 phases, the residual high-ordered carbon and Fe_2P with outstanding electric conductivity in the nanocomposite.