1. Lithium Battery Hazards
Julie Banner
Code 616
Naval Surface Warfare Center
Carderock Division
System Safety Society WDC Chapter Mtg
16 March 2011

2. Background & Outline
Information included in this presentation is unclassified
The purpose of this presentation is to provide general information covering
Basic introduction to lithium battery technology
General hazards associated with lithium batteries
Firefighting methods and lithium batteries
Recent developments in the Navy’s Lithium Battery Safety Program
Some of the images shown in this presentation are the extreme results of aggressive and deliberate battery abuses
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NSWC Carderock Code 616

3. Lithium Batteries Used by the Navy
Battery Types
Primary
Active
Reserve
Liquid Reserve
Thermal
Secondary
Cell Designs
Bobbin
Spiral
Bipolar
Coin
Prismatic
Battery Chemistries
Cathode
Manganese Dioxide
Carbon Monofluoride
Thionyl Chloride
Sulfur Dioxide
Sulfuryl Chloride
Vanadium Pentoxide
Cobalt Oxide
Anode
Lithium Metal
Lithium Alloy
Lithium Ion
Electrolyte
Organic Liquid
Polymer/Gel
Cell Sizes
Button Cell (0.01 Ah)
AA-Size Cell (2 Ah)
D-Size Cell (10-20 Ah)
Specialty Design Cell (2,200 Ah)
Air Force Design Cell (10,000 Ah)
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4. Table of Battery Characteristics
From Handbook of Batteries, 3rd Edition, by Linden and Reddy
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5. Delivered Power & Energy Comparisons
UUV Long Term Goal exceeds capability of today’s state of the art power sources
Lithium Ion
Zn-air
Specific Energy, Wh/kg
1375 Wh/kg = TNT
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6. State-of-the-Art Lithium Cells
Different electrochemistries (electrolyte, cathode materials)
Different cell designs ==== Different performance and safety characteristics
Different packaging
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7. Batteries Are Stored Chemical Energy
Controlled Release of This Energy Provides Electrical Power in the Form of Current and Voltage
Uncontrolled Release of This Energy can Result in Venting, Fire, Release of Toxic Materials, Shrapnel, High Pressure Events, Deflagration (with or without Report) and Many Combinations Thereof
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8. Lithium Battery Hazards
Venting
Leaking of hazardous materials
Noxious or acidic gases
Strong acids
Flammable gasses and liquids
Fire
Note: Other types of batteries may also respond to abusive conditions presenting similar (but not identical) hazards, so many of the handling and safety recommendations that follow can be considered to be appropriate for all battery types
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9. Venting
Release of internal pressure from a cell by ejecting some or all of its internal components into the environment
These components may be flammable and may include noxious gasses
A venting of a lithium ion battery may release
Flammable organic electrolyte (e.g. PC-EC-DMC)
LiPF6 -- this material is reactive with H20 and forms HF
Carbon either as carbon or water reactive lithiated graphites
LiNiCoO2 or other lithiated oxides and heavy/transition metals
Metal foils and fragments (copper or aluminum)
Methane, hydrogen, carbon monoxide (electrolyte decomposition products)
Ventings may be accompanied by smoke, sparks and or flames
Ventings may be high pressure events
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NSWC Carderock Code 616

10. Hazards Vary…
Release of internal pressure from a cell by ejecting some or all of its internal components into the environment
A venting of a Li/SOCl2 battery may release
Lithium Metal (Li) - reactive in air & highly reactive in H2O
Thionyl Chloride (SOCl2) - combines immediately with any moisture to create fumes of HCl and SO2
Carbon (C)
Aluminum Chloride (AlCl3)
Lithium Chloride (LiCl)
PVC
PTFE (teflon)
Ventings may be accompanied by smoke, sparks and or flames
Ventings may be high pressure events
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11. Likely Mistreatment Scenarios
Physical abuse, such as crushing, puncturing or burning
Overcharging a rechargeable lithium battery (due to electronics failure)
Charging of primary (non-rechargeable) batteries
Exposure of battery to inappropriate environment
High temperature abuse (140°C)
Water immersion of an unprotected or unsealed battery
Short circuit or abnormally high rate discharge of battery
Unanticipated latent manufacturer’s defect failure
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12. Physical Abuse
Puncturing and crushing result in massive internal short circuits that are not mitigated by external or internal safety devices and frequently result in thermal runaway and violent venting of lithium batteries with incandescent ejecta
Recommendation: Whenever possible, package lithium batteries in protective containers and be aware of potential physical hazards
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13. Overcharging
Lithium ion batteries may be designed to be recharged either inside or outside their system housing
Redundant over-voltage and over-current electronics “should” prevent abuse due to overcharging
In abuse tests of high energy lithium ion cells and similar modules, cells vented with pressure and flame in response to extreme overcharging conditions
Recommendation: Always follow standard operating procedures and manufacturer recommendations for charging the battery
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14. Short Circuit
Use of battery in circuit with very low (<50 milliohms or less) resistance
Short circuits can be caused by
Connecting positive and negative terminals of battery (External, i.e. “crowbar” or loose wires or screwdriver)
Breaching physical integrity of battery (Internal)
Fuses and other over-current electronics “should” prevent abuse due to external short circuits
Some lithium cells include internal safety devices to protect against overcurrent conditions
Precautions include
Do not handle battery modules on metal surfaces
Keep terminals insulated and separated
Never remove or bypass electrical fuses
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NSWC Carderock Code 616

15. Lithium Battery Firefighting Guidance
System-specific guidance included in system emergency documentation
General shipboard guidance given in S9086-S3-STM-010 “Naval Ships’ TM Chapter Volume 1 Surface Ship Firefighting” Vol 1 Rev 13 of 1 Jan 2010, section 8.14
Application of a narrow-angle fog of water or AFFF is the preferred method to cool the battery, suppress immediate fire output, and reduce likelihood of propagation to remaining cells
Maintain an adequate distance for personnel safety from exposure to fireballs and/or projected fragments
Personnel should wear SCBAs to protect from exposure to hazardous gases (acid gases, oxidizers and other toxic and irritating materials)
Continue to cool the battery for several minutes after the last cell event and do not approach until there is evidence that all reactions have stopped
Initiate active desmoking/ventilation of the area as soon as practicable during the casualty to remove heat, smoke and toxic gases
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16. Documentation for the Navy’s Lithium Battery Safety Program
Instruction -- Defines the Process
NAVSEAINST 9310 Initial Release in 1979
NAVSEAINST a of 11 March 1982
NAVSEANOTE 9310 of 11 June 1985
NAVSEAINST b of 13 June 1991
NAVSEAINST c revision in review at NOSSA & planned for an FY11 release
Technical Manual -- Guidelines for Design, Review and Procedures for Testing
Technical Manual for Batteries, Navy Lithium Safety Program and Procedures, Rev 2 S9310-AQ-SAF-010 of 15 July 2010
Default.aspx
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17. “Just Gimme the Approved Battery List…”
Navy Lithium Battery Safety Authorizations are system specific
Authorizations for previously reviewed batteries:
Leverage data from previous programs (testing, analysis, design) when appropriate
Do not required duplicative testing
Are usually quicker
Contact NOSSA, Carderock or Crane to determine if a battery has previous safety reviews on file
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18. Oversight Authority for the Navy’s Lithium Battery Safety Program
Originally granted to NAVSEA Safety Division (NAVSEA 665), and has followed the Explosive Safety Office through multiple reorganizations
Currently resides with Code N84 of the Naval Ordnance Safety and Security Activity, under the auspices of the Explosive Safety Office for Navy Systems
Special Authority for specific platform use
NAVSEA Code 05Z34 for Surface Ship & Submarine Carriage
MSCHQ for Military Sealift Command platforms
NAVAIR for Aircraft Carriage
Primary testing and evaluation sites
Carderock Division, NSWC, Code 616
Crane Division, NSWC, Code GXS
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19. Status of SEA05Z Lithium Battery Ship Integration Process
Official documentation (signed) is the NOSSA Interim Letter of 2 April 09
SEA05Z34 proposed process is contained in draft TM “High-Energy Storage System Safety Manual”
Released 9 Jul 10 for review
Revised version has been in review by SEA05 (Mr. Drakely and ADM Eccles) for past few months
Under a mandatory 15 day SEA05Z34 official standards review
Staged implementation of SEA05 TM is planned
New manual will be implemented on new system starts as of the issue date
Approvals currently in process will follow interim guidance except the MIL-STD 882 assessment will follow new manual guidance
Approval extensions are TBD

20. Draft High-Energy Storage System TM - Goal & Scope
Characterize the safety hazards and risks associated with integration and use of lithium batteries aboard Navy platforms
Determine if use of platform features (fire fighting, special stowage, charging capabilities) mitigates risks associated with batteries and identify unmitigated risks
Scope
“Includes all lithium batteries used, carried, or intended for use or carrying on Navy platforms, both as standalone batteries and as systems incorporating lithium batteries. Specifically included are manned Deep Submergence Systems (DSS).”
Scope as written does not have universal acceptance at top levels in NAVSEA

21. Draft High-Energy Storage System TM - Documentation Requirements
Initial Data Submission
Top Level Requirements (TLR) List
Operational Requirements Document (ORD)
Preliminary Hazard List (PHL)
Concept of Operations (CONOPS)
Secondary Data Review due prior to PDR
Program Management Plan
Memorandum of Agreement with SEA05, battery tech agent and program stake-holders
Hazard Log
Preliminary Hazard Analysis (PHA)
Failure Modes and Effects Analysis (FMEA)
Approved Documentation to Proceed to FDR/Fleet Release
Battery Test Plan
Test Report
Safety Hazard Analysis (Final)
Manufacturing Audit Report
Note: For projects that are not formal acquisition projects SEA05 will accept equivalent documents.
For instance if there is not a formal TLR list or ORD, alternative formats would be accepted.

22. Draft High-Energy Storage System TM - Test Requirements
Require extensive customization of testing with in- depth input & direction from SEA-05Z, SEA-05P, and other cognizant platform warrants
NOTE: This is an all inclusive matrix and many test can be combined into one test by proper design

23. Critical Design Attributes for Shipboard Carriage
Contain severe casualty output and limit consequences to personnel & platform
Target mitigations to Maximum Credible Event (MCE)
Review data from Worst Case Event (WCE) as part of the risk analysis
Proven battery management systems
Demonstrate reliability & redundancy or inherent fault tolerance
In some cases (platform dependent) software validation IAW Fly-by-wire criteria is mandatory and will be conducted by joint review
Automated and validated warning systems
Industrial standard systems preferred to those with limited access (proprietary)
Software validation may apply
Fire suppression and ventilation tactics and systems that are compatible with the platform capabilities & personnel
Focused on MCE level as demonstrated by test or simulation
Based on system and host platform safety precepts for operability

24. Conclusions
Within the group known as lithium batteries, there are a wide variety of specific performance and safety characteristics
Specific lithium battery hazards depend on both battery and system- related variables
The major classes of hazards associated with most lithium batteries include
Venting of noxious and/or hazardous gases
Fire
High pressure events
When fighting a lithium battery fire, cooling (water) is key and smothering (heavy gas or chemical blanket) is not generally effective, therefore Navy safety guidance recommends the use of water or AFFF as the extinguishing media for lithium battery fires
The Navy’s Lithium Battery Safety Program strives to minimize risk to personnel and platforms while allowing the use of lithium batteries on our ships, aircraft and submarines to advance our military capabilities through the approval process managed by NOSSA
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NSWC Carderock Code 616

25. Got a Lithium Battery? Who U Gonna Call? Julie Banner
NSWC Carderock, Code 616
(301) desk/voic
(240)
(301) fax
(240) alternate fax
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NSWC Carderock Code 616