U.S. DOE Perspective on Lithium-ion Battery Safety

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U.S. DOE Perspective on Lithium-ion Battery Safety David Howell US Department of Energy Washington, DC Technical Symposium: Safety Considerations for EVs powered by Li-ion Batteries The National Highway Traffic Safety Administration May 18, 2011 The Parker Ranch installation in Hawaii 1 Energy Efficiency and Renewable Energy eere.energy.gov

Outline Program Overview Safety and Abuse Tolerance Activities DOE Safety/Abuse Testing Battery Design & Modeling Materials R&D Vehicle Testing Collaborations Summary & DOE Perspectives 2 Energy Efficiency and Renewable Energy eere.energy.gov

Separator Programmatic Structure MISSION: Advance the development of batteries to enable a large market penetration of hybrid and electric vehicles to achieve large national benefits.. Energy Storage R&D $93 M Exploratory Materials Research 25% Applied Battery Research 20% Battery Development 45% Testing, Analysis & Design 10% e e Anode Cathode e Li + New Materials Research Diagnostics & Modeling Electrochemistry Optimization Power & Capacity Life, Improvement Next Generation Cell Development Performance & Cost Reduction Standardized Testing Life Projections Design Tools 3 Energy Efficiency and Renewable Energy eere.energy.gov

Major Technical Challenges and Barriers Cost Specific Energy/ Energy Density Safety Barrier/Challenge Reduce Cost Significantly Increase Energy Density (3 rd generation lithium-ion, lithium-sulfur, lithium-air) Potential Solutions Improve material and cell durability Improve energy density of active materials Improved manufacturing processes Improved design tools/design optimization Develop ceramic, polymer, and hybrid structures with high conductivity, low impedance, and structural stability Select improved electrolyte/separator combinations to reduce dendrite growth Improve Abuse Tolerance (High energy density, reactive materials, flammable electrolytes) Implement battery cell and pack level innovations (e.g., improved sensing, monitoring, and thermal management systems) Implement battery materials innovations (e.g., nonflammable electrolytes, high-temperature melt integrity separators, additives & coatings) 4 Energy Efficiency and Renewable Energy eere.energy.gov

Battery Cell Form Factors Battery Pack with Prismatic Cells Battery Pack with Cylindrical Cells Courtesy: A123Systems Courtesy: Johnson Controls Inc. 5 Energy Efficiency and Renewable Energy eere.energy.gov

Safety/Abuse Tolerance Testing Abusive Conditions Mechanical (crush, penetration, shock) Electrical (short circuit, overcharge, over discharge) Thermal (overheating from external/internal sources) Abuse Testing Methodology SAE Abuse Test Manual J2464 Several members of the VTP Team participated on the committee to develop the new SAE Abuse Test Manual Facilities: Sandia National Laboratories was awarded funding through the American Reinvestment and Recovery Act (ARRA) for facility upgrades to the Battery Abuse Testing Laboratory. Improving the safety engineering controls and systems required to accommodate abuse testing PHEV and EV sized batteries, Updating laboratory equipment and systems to facilitate the growing demand for safety testing. CT image of an 18650 Li-ion cell with a large defect in the roll 6 Energy Efficiency and Renewable Energy eere.energy.gov

Test Methods Development On Demand Internal Short Circuit Test Development Many field failures are caused by internal shorts resulting from manufacturing defects or foreign particles inadvertently incorporated in the cell during manufacture. The internal short could lead to thermal runaway and severe reactions. DOE has funded multiple projects to develop techniques to mimic internal shorts on demand. The purpose of the work is to develop a tool or technique that will be used to develop methods to detect and mitigate internal shorts. Techniques under development include Low-melting point metal alloys used to trigger ISCs at relatively low temperatures (SNL and NREL) Pinch test using spherical balls (ORNL) Proprietary method (TIAX) Preliminary experimental demonstration of differences in ISC severity based on short type (current collector-current collector, current collector-active material) Experimental data will be incorporated in thermal models developed by NREL and TIAX. Reproducibility needs to improve for all methods 7 Energy Efficiency and Renewable Energy eere.energy.gov

Aged Cell Testing Impact of Cell Age on Abuse Response Accelerating Rate Calorimetry (ARC) ARC profiles plotted as heating rate as a function of temperature for the fresh cell (in blue) and 20% faded aged cell (in green) populations. 8 Energy Efficiency and Renewable Energy eere.energy.gov

Battery Development Efforts to Improve Safety United States Advanced Battery Consortium (USABC) The United States Advanced Battery Consortium (USABC) is a collaborative effort among Ford, GM, Chrysler and DOE to develop advanced automotive batteries. Abuse tolerance is among the barriers being addressed. The cell materials technologies being developed are: Safety reinforced separators Ceramic filled separators High temperature melt integrity separators Coatings on high voltage cathodes Cathode additives to improve abuse Electrolyte additives to mitigate overcharge Heat resistant layers on anode and cathode electrodes AlF 3 coating layer for cathodes 9 Energy Efficiency and Renewable Energy eere.energy.gov

Battery Development Efforts to Improve Safety USABC Cell and Abuse Tolerance Improvement Efforts Work at cell & pack level also includes improving abuse tolerance. Technologies being developed: Charge interrupt devices Cell vent designs to release electrolyte gasses prior to thermal runaway System designs that manage vented gasses away from passenger areas Liquid and gas, active and passive, thermal management systems Simulations to evaluate abuse tolerance mitigation technologies at the cell and system level Schematic of Prismatic Cell Gasket Safety vent Cathode lead CID Terminal plate Insulator Separator Cathode pin Cathode Top cover Insulator case Spring plate Anode can Anode Wound or Stacked Electrodes 10 Energy Efficiency and Renewable Energy eere.energy.gov

Battery Design & Modeling Computer-aided Engineering of Batteries (CAEBAT) Develop computer-aided engineering (CAE) tools for the design and development of battery systems for electric drive vehicles Develop and incorporate existing and new models into a battery design suite to reduce battery development time and cost while improving safety and performance Include CAE tools to predict and improve safety of cells and battery packs Battery design suite must address multiscale physics interactions, be flexible, expandable, and validated Atomistic Scale Physics of Li-ion Battery System in Different Length-Scales Charge balance and transport Electrical network in composite electrodes Li transport in electrolyte phase Li diffusion in solid phase Interface physics Particle deformation & fatigue Structural stability Scale of Particles Thermodynamic properties Lattice stability Material level kinetic barrier Transport properties Element 1 Component Level Models Scale of Electrodes Scale of Cells Electronic potential & current distribution Heat generation and transfer Electrolyte wetting Pressure distribution CAEBAT Overall Program Element 2 Cell Level Models Scale of Modules Thermal/electrical inter-cell configuration Thermal management Safety control Element 4: Open Architecture Software Scale of System System operating conditions Environmental conditions Control strategy Element 3 Battery Pack Level Models 11 Energy Efficiency and Renewable Energy eere.energy.gov

Battery Safety Abuse Modeling Thermal Response and Short Circuit Modeling EC-Power : thermal response, full and partial nail penetration, shorting by metal particle NREL, Tiax: thermal response, and internal short circuit models Structural Crash Models University of Michigan (USCAR funding) developing a mechanical constitutive analytical model and a numerical simulation model. Sandia National Labs (DOE funding) validating the models Future R&D to develop safety modeling that combines electrochemical-thermal coupled models with mechanical material models. Diameter = 0.5 mm T max =180 o C T max =58 o C T avg = 34 o C T avg = 53 o C 0.5s T max -T avg =146 o C 10s T max -T avg =5 o C 100s Diameter = 8 mm T max =36 o C T avg = 34 o C T max -T avg =2 o C Full Penetration T max =52.8 o C T avg = 52.3 o C T max -T avg =0.5 o C 0.5s 10s 100s T max =116 o C T avg = 113 o C T max -T avg =3 o C T max =114 o C T avg = 112 o C T max -T avg =2 o C 12 Energy Efficiency and Renewable Energy eere.energy.gov

Normalized Rate (C/min) Materials R&D Cathodes with Improved Stability 400 350 300 250 200 150 100 50 0 Accelerating Rate Calorimetry (ARC) LiCoO 2 Gen2: LiNi 0.8 Co 0.15 Al 0.05 O 2 Gen3: Li 1.1 (Ni 1/3 Co 1/3 Mn 1/3 ) 0.9 O 2 LiMn 2 O 4 LiFePO 4 0 100 200 300 400 Temperature (C) EC:PC:DMC 1.2M LiPF 6 Increased thermal-runaway-temperature and reduced peak-heating-rate for full cells Decreased cathode reactions associated with decreasing oxygen release 13 Energy Efficiency and Renewable Energy eere.energy.gov

Normalized Rate (C/min-Ah) Materials R&D (cont d) 200 180 160 140 120 100 80 60 40 20 Cathode coatings and novel electrolytes Thermal Response of AlF 3 -coated Gen3 cathode in 18650 cells by ARC 18650 Full Cell ARC for Gen3 and AlF 3 -coated Gen3 0 Gen3 4.1 V, 876 mah 50 150 250 350 450 550 Temperature (C) AlF 3 -coated Gen3 4.1 V, 637 mah Anion Boron Receptor Electrolyte AlF 3 -coating improves the thermal stability of NMC materials by 20 C Improves thermal response during cell runaway 50% reduction in total heat output of NMC 433 with LiF/ABA electrolyte compared to standard electrolyte, Reduce gas generation and decomposition products 14 Energy Efficiency and Renewable Energy eere.energy.gov

DOE Fleet Testing Safety Experience DOE s Advanced Vehicle Testing Activity tests and collects data on electric drive vehicles (EDVs) using conversion, prototype, and production vehicles, some with Li-ion batteries. In 2011, data was collected for 6,500 vehicles over trips covering more than 26 million miles in EDVs with almost no adverse events. Three thermal events have occurred in non-production vehicles in recent years. 15 Energy Efficiency and Renewable Energy eere.energy.gov

DOE Fleet Testing Safety Experience Vehicle 1 Vehicle 2 Vehicle 3 Type HEV converted into a PHEV by adding a 12 kwh Li-ion pack Event Battery received 13.5kWh overcharge Significant smoke, heat, but no flame evidence Battery cells remained in place Components (pouch bag, solvents, separator) with low melting points were missing Cause Likely a faulty charger or BMS HEV converted into a PHEV : NiMH pack with a 5kWh Li-ion pack Vehicle fire Converter design deviated from battery manufacturer design guidelines The first responders had easy access to the battery, significant damage occurred to the pack and the vehicle before they arrived Likely caused by improper assembly of bolted joints with electric lugs PHEV with a 12kWh pack Significant smoke, heat, but no flame evidence The first responders sprayed significant volumes of water into the vehicle to extinguish the melting seat and carpeting Pack resumed smoking and significant heat rise. Testing indicated one module had high voltage Load bank was used to discharge the high voltage module and stabilize battery. Most likely cause of the failure was faulty wiring design. 16 Energy Efficiency and Renewable Energy eere.energy.gov

DOE Fleet Testing Safety Experience Summary Damage can be limited if responders have good access to the battery pack Full battery discharge/thermal event can continue over multiple days Issues to consider with PHEV battery and vehicle design Lack of common disconnect locations Responders unaware of hazards Electrical safety personal protection equipment (PPE) and breathing apparatus should be worn by first responders Access to battery pack is critical IF an event occurs 17 Energy Efficiency and Renewable Energy eere.energy.gov

Intra Government Collaborations DOT/NHTSA Technical support for Regulations for battery transportation Collaboration on Battery Safety tests with NHTSA and NSWC DOE/DOT/INL is working with the National Fire Prevention Association to develop PPE needs and first responder training aids. We are filming multiple lithium battery test burns with multiple suppression methods utilized Joint studies, working groups Volt battery pack being prepared for test eere.energy.gov

DOE Perspective Regarding Lithiumion Battery Safety Safety of Batteries is of Central Importance Safety is a key barrier to introduction of rechargeable batteries into vehicles. Vehicle environment is challenging (temperature, vibration, etc.) Large cells and large capacity batteries for vehicle traction present additional challenges Safety is a systems issue, with many inputs and factors. Even safe cells and batteries can prove unsafe in some applications due to poor engineering implementation or an incomplete understanding of system interactions. Standardized tests are crucial to obtain a fair comparison of different technologies and to gauge improvements. eere.energy.gov