Fire Hazards Of Lithium Ion Batteries
International Aircraft Systems Fire Protection Working Group MeetingDresden, Germany, May 12-13, 2015Fire Hazards of Lithium Ion BatteriesRichard E. Lyon, Richard N. Walters, Sean Crowley,and *James G. QuintiereFEDERAL AVIATION ADMINISTRATIONAviation Research DivisionWilliam J. Hughes Technical CenterAtlantic City International Airport, NJ 08405*Department of Fire Protection Engineering,University of Maryland, College ParkWEB: www.fire.tc.faa.govE-MAIL: richard.e.lyon@faa.gov
Objective: Measure Fire Hazards of LIBsTypicalpackagingTypical bulk shipment as cargoPassenger electronics
Causes of Battery Failure Thermal– Separator melts due to hightemperature causinginternal short circuit thatreleases heat.– Contents mix, react andthermally decompose. Electrical– Overcharge– Rapid discharge Mechanical– Physical damage (puncture)– Manufacturing defect orcontaminant 1 secondAll lead to auto-accelerating heatgeneration and rapid temperatureincrease (Thermal Runaway) leadingto fire and/or explosion
Materials: Commercial 18650 LIB Cells18650 Rechargeable Cells ( 44 grams each)65 mm18 mm
Electrical Properties of Tested CellsMaximumCapacity,Qmax(A-s)CathodeCell Potential, (V)- G, hemical Energy Available to Do Useful Work (Free Energy), G - QState-of-Charge, SOC Q/Qmax
Experimental Methods: Cell Charging Charge / Discharge 4 cells simultaneously Record: charge / discharge capacity Programmable for different states of charge
Methods: Hazard MeasurementsEnergetics of Cell FailureASTM D 5865-14, Standard Test Method forGross Calorific Value of Coal and CokeThermal Effects of Cell FailurePurpose-Built Thermal Capacitance(Slug) CalorimeterFire Behavior of Lithium Cells(ASTM E 1354, Standard Test Method for Heat and VisibleSmoke Release Rates for Materials and Products Using anOxygen Consumption Calorimeter)
Bomb Calorimeter (ASTM D 5865) Parr Instruments Model 1341 Plain Jacket Oxygen Bomb Calorimeter Resistance heating to force thermal runaway of LIBs Nitrogen blanket (1 Atm) to prevent oxidation of contents after failure Temperature, voltage and current logged for all testsExperimental SetupBomb and other componentsfor 18650 battery tests
Thermodynamics of Cell FailureDepends oncell chemistry UTotal Urxn QTotal energyreleased at cellfailure(measured in bomb)Electrochemical (Free) energy release(Calculable from cell potential (V) andcharge Q (A-s))Energy released by mixing, chemicalreaction and thermal decompositionof cell components.
Analysis of Bomb Calorimeter Data18650 Cell ChemistryEnergy Release at Failure otal Energy( Utotal)LiMn2O4-LiNiCoO2Energy of Mixing, Reactionand Decomposition, Urxn Urxn 90% of QFree Energy, G ( Q)05001000150020002500Charge, Q (mAh)30003500
Energy Release at Failure (kJ/cell)Energetics of Individual Cell FailureLiMn2O4-LiNiCoO280706050403020100 Utotal Urxn0401020304050LiNiCoAlO260 Utotal3020 Urxn100-100510152025LiCoO26050403020100-10 Utotal Urxn0302520151050-5510 15 20 25 30 35 40Unknown Utotal Urxn0510Electrochemical Free Energy, Q (kJ/cell)1520
State-of-Charge is Not a Good Predictor of Energetics forDifferent Chemistries and Cell PotentialsFree Energy, Q y( Utotal)80LiMn2O4LiNiCoO2Total Energy, Utotal (kJ/cell)StoredElectrochemicalEnergy ( wn201000020 40 60 80 100State of Charge, Q/Qmax (%)020 40 60 80 100State of Charge, Q/Qmax (%)
Li-Ion 18650 Batteries - Post TestZero Charge50% Charged100% Charged
Gravimetric Analysis for Volatile Yield Bomb weighed before and after ventingto atmosphere to determine volatile yield Volatiles are combustible Yield QVolatile Yield, wn01020304050Electrochemical (Free) Energy, Q (kJ/cell)
Infrared Spectra of Gaseous Decomposition ProductsLiNiCoAlO2LiCoO2LiMn2O4LiNiCoO2Unknown
Thermal Effects of Cell FailureSeparatorMelts (150 C)20 g2sVenting (200 C)Failure (250 C)600 C2sJ.G. Quintiere & S.B. Crowley, Thermal Dynamics of 18650 Li-ion Batteries, TheSeventh Triennial International Fire & Cabin Safety Research Conference,Philadelphia, PA, 2013.
Thermal Energy Release (qb) Free Energy ( Q)Thermal Energy qb, kJ/cellImplies chemical reactions of electrolytes( Urxn) take place outside of cell whencontents are ejected5040302011010010203040Stored Free Energy, Q (kJ/cell)50
Adiabatic (Surface) Temperature RiseTmax Tf U total U rxn Q Tf mcpmcp mcp U rxn Qmax SOC 250 C *mcpmcp100Maximum Cell SurfaceTemperature, Tmax ( C) 140012001000ContentsEjected, Urxn 0,Tmeas Tcalc 80060040020000204060State of Charge/SOC (%)80100
Fire Calorimeter Testing of Lithium CellsStandard ASTM E 1354 OperationSpecial holder designed toprevent rocketing of cell at failure
Heat Release Rate in Cone CalorimeterFailure is so rapid that HRR must becorrected for cone calorimeter response6FailureHRR, kW/cell55sVenting5s4HRR Corrected for 3second Response Time ofCone Calorimeter(Deconvoluted)5s32Original Data108090100110120130Elapsed Time, seconds140150
Fire and Thermal Hazards of 18650 CellDischarge of StoredElectrochemical EnergyBy Internal Short Circuit(14 kJ/cell)Total 103 kJ/cell 2.3 kJ/g 1/20 jet fuelFlamingCombustion ofCell Contents(75 kJ/cell)qv 75 kJ/cell6.62 x 10-5 m3/ cell 109 J/m3DecompositionReactions(14 kJ/cell)LiCoO2 Cell at 50% SOC
Analytic Model of 18650 Cargo Fire GrowthL(t)CombustionVolume at time t,V(t ) L(t )3L(t)L(t)Effective Length of 18650,L (18mm)(65mm) 34mmConstant linear fire growth rate, L2L 0 3x10 4 m / s mc / LHeat Release in Flaming Combustion, qv 109 J/m3 dVdL(t )3HRR (t ) qv qv 3qv (L0 )3 t 2dtdt
Model Versus Full Scale Test DataHeat Release Rate, HRR (kW)Class EMain DeckCargoFull-Scale Test (Before)Full-Scale Test (After)12001000Battery Fire t 2 Model(LiCoO2 18650, 50% SOC)800600Full Scale Test DataLiCoO2 18650, 50% SOC(from O2 consumption)H. Webster, May 201340020000102030405060Time After First Ignition, minutes70
SummaryState-of-charge is a poor predictor of fire hazard fordifferent batteries and cell chemistries.Total energy at failure of Li Ion cells/batteries (LIB), Utotalis almost twice the stored electrochemical energy Q forthe 18650 cell chemistries of this study.
Richard E. Lyon, Richard N. Walters, Sean Crowley, and *James G. Quintiere . Objective: Measure Fire Hazards of LIBs Passenger electronics Typical packaging Typical bulk shipment as cargo . Causes of Battery Failure
1. Are all lithium-ion batteries created equal? — NO 2. Are all chemistries the same? — NO 3. Are all batteries using the same lithium-ion chemistry the same? — NO 4. Do all lithium-ion batteries have similar cycle life, like Flooded Lead Acid (FLA)? — NO 5. Can I use any lithium-ion battery in my equipment? — NO 6.
14-100508-000 Assy. Lithium Battery, 30 Ahr 14-100508-900 Assy. Lithium Battery, preown 30 Ahr 14-100957-002 Assy. Lithium Battery, w/ jumper 48 Ahr 14-100957-004 Assy. Lithium Battery, w/ jumper 30 Ahr 14-100957-904 Assy. Lithium Battery, preown 30 Ahr 14-860202-002 Pkg. Envoy, Lithium, with ACDC 115V 14-860202-004 Pkg. Envoy w/ Lithium .
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polyatomic ions: a. amm onium ion b. sulfate ion c. sulfite ion d. carbonate ion e. nitrate ion f. permanganate ion g. hypochlorite ion h. phosphate ion i. cyanide ion j. hydroxide ion 9.2 Naming and Writing Formulas for Ionic Compounds A. _ Ionic Compounds 1. What are Binary Ionic Compounds? 2.
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