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1 Pipeline and Hazardous Material Administration (PHMSA) Department of Transportation AN OVERVIEW OF INTERNAL SHORT CIRCUIT SCREENING TEST METHODS FOR LITHIUM BATTERIES and a Proposal for Test T.6 Modification Presented at 1st Workshop on Lithium Batteries, Brussels, Belgium March 17-18, 2015 Steve Hwang, Ph.D. [email protected] 2 UN Test Guidelines Tests Test Name T1 T2 T3 T4 Altitude Thermal Vibration Shock T5 T6 T7 T8 Purpose Requirement Vacuum @ 11.6 kPa 1 -40 – 72 oC 1 7 Hz – 200 Hz 1 Small 150 g 6 ms 1 Large 50 g 11 ms External Short External short 2 Impact/Crush Internal short by 2 applying external impact Overcharge <18 V 3 > 18 V x 1.2 Forced Discharge Maximum discharge 3 current 1. No leakage, no venting, no disassembly, no rupture, no fire, <90% of V 2. Not exceeding 170 oC, no disassembly, no rupture, no fire 3. disassembly, no fire Primary Cell Battery yes yes yes yes yes yes yes yes Secondary Cell Battery yes yes yes yes yes yes yes yes yes yes yes no yes yes yes no no no no yes yes no yes no 3 Causes of Internal Short-Circuiting Causes Why can this happen? 1. Shock or Dropping 2. Formation of Dendrite 3. Existence of Impurities due to Poor Quality Control during Manufacturing 4. Imbalance of Voltage among Cells 5. High Charging Voltage applied to a cell 6. Propagation of Thermal Runaway Physical Abuse Lithium Plating Manufacturing defects 7. Separator Failure Can it be managed? Strong casing by design New Techniques needed New Techniques needed Voltage BMS Imbalance High Charging BMS Voltage Damaged Cell Proper venting, insulation can raise temp. of surrounding cells Temp, Defects, wearT control, quality out, puncture, degrad. control, struct. 4 Cases of Thermal Runaway as it relates to Internal Shorts • Nail Penetration - Did not cause thermal runaway • Manufacturing Defects – Possible thermal runaway (Metal particle in cathode slurry) • Cell Crushing - Can cause massive internal shorts and thermal runaway • Metal Plating (Dendrite) - Can reach 200 oC with thermal runaway • Elevated Temp - Can cause thermal runaway @ >170 oC 5 Comparison of Internal Shorts Screening Tests How Applied • NREL During Manufacturing ISC Device Process • UL Indentation Rounded Tip Induced ISC Nail • IEC (62133) Nickel Powder Forced ISC Tech • Nail Nail Penetration • Impact/Crash Small: Steel Bar (UN 38.3) Large: Flat Surface • Propagation Insulated Test Thermal Chamber 1. No Fire 2. No fire, No disassembly , not exceeding 170 oC 3. No external fire, No battery case rupture Method for Inducing ISC As a Test Requirement for Prevention Heat to ~55 oC Can reduce IS with 1 to Melt Wax Shut-down Separator Pressure Safety Level req’d 1 in the Market Pressure Safe Cell Design 1 Piecing Drop weight Force applied Heating of a Cell Safety Level req’d in the Market Survival of Deformation Proper Venting 1 2 3 6 7 8 Cell Separator Deformation from Indentation Test 9 Data Search Test Type (Li Ion cells) Indentation ISC % of Explosion or Fire 58 Forced Nickel Powder None NREL ISC Device Depending on existence of shut-down separator Techniques 10 -10 oC DENDRITE GROWTH PATTERN 5 oC 20 oC 11 separator cross-section Separator vs. Dendrite Mechanical Interaction: Mixed Penetration Polymer Property: Elastic, Softened Failure Mode*: Conductive Matrix of Li0 Particles Desire Property: High Puncture Strength Ideal Material: Small Pore Size Mechanical Interaction: Puncture Stress Polymer Property: Ductile-to-Brittle Transition Failure Mode*: Hard Short Pierces Separator Desire Property: Puncture Strength & Elastic Modulus Ideal Material: Biaxial Orientation Mechanical Interaction: Compressive Stress Polymer Property: Brittle Failure Mode*: Crack Propagation & Growth Desire Property: High Bulk Modulus; Low Compressibility Ideal Material: Large Pore Size OK; High Ductility 12 SUMMARY • • • • • Many companies are testing cells and batteries to determine their integrity as it relates to ISC using the test methods of their choosing. None of the ISC screening methods can address the basic concern on IS prevention. It is not clear why these tests are conducted by he manufacturers. No recommendable test methods for preventing occurrence of ISC can be identified from literature search. Though many field failures are reported to be caused by IS resulting from manufacturing defects or impurities inadvertently incorporated during manufacturing, no tools presently exist to detect or mitigate these defects. 13 SUMMARY (cont’d) • Recent research information indicates that dendrite formed at the anode migrates to the cathode through the separator membrane to cause an internal short circuiting. • A corollary to the finding is that the integrity of separator membranes plays a significant role in retarding or preventing the dendrite penetration through the membrane. • It is important to test for the desired mechanical properties of the separator membranes to mitigate the occurrence of internal shortcircuiting and thermal runaway.