9000 Virginia Manor Rd Ste. 290, Beltsville MD 20705 | 301-474-0607 | www.dfrsolutions.

com
© 2004 – 2010
 How to Prevent Li-Ion
Battery Failures
Vidyu Challa, PhD
Technical director, DfR Solutions

2 9000 Virginia Manor Rd Ste. 290, Beltsville MD 20705 | 301-474-0607 | www.dfrsolutions.com

© 2004 – 2010
 OUTLINE
o Samsung 2016 Root Cause Analysis
o Battery failure mechanisms and modes – pathway to thermal runaway
o Battery protection mechanisms
o Internal and External
o Mitigation methods
o Design
o Manufacturing
o Battery Management System
o Application Assembly, and Storage
o User
o Summary
3
 Li Ion Battery Working Mechanism
o Anode negative electrode, cathode positive electrode
o Lithium ion is an intercalation battery (‘rocking chair
mechanism’)
o insert between layers or in crystal structure

4
 Solid Electrolyte Interphase
o Solid electrolyte interphase (SEI) formed during first few
charging cycles
o SEI can be unstable outside operating window
Graphite Anode SEI Organic Electrolyte

5
 Samsung 2016 Battery
Failures

Source : Samsung Galaxy Note 7 failure investigation press conference, Jan 2017. All Information in public
domain

6
6
 Samsung Galaxy 2016 Failures
o Galaxy Note 7 fires were reported within a few weeks of the
product launch.
o Samsung recalled affected phones, and pointed to a
manufacturing error from its battery supplier Samsung SDI.
o The batteries were swapped with ones from its Chinese
supplier ATL.
o Replacement phones that were supposed to be “fixed” also
started to catch on fire.
o Samsung scrapped the entire product line. 2.5 million phone
recalls prior. Cost Samsung $5 Billion
7
 Flattened Jellyroll Pouch Cell Design

8
 Manufacturer A Root Cause
o Damage to the negative electrode windings caused by
deflection by a pouch design that did not provide sufficient
volume to accommodate the electrode assembly.
o Curvature of pouch causes deflection of the negative electrodes.

9
 Negative Electrode Deflection
o Negative electrode damage provides multiple pathways to cell internal
short circuit and thermal runaway under normal cycling conditions
o Damage to the separator
o
Lithium plating

Source : Information in public domain

10
 Overcrowded Bus Analogy

11
 Manufacturer B Root Cause
o Tab welding defect created an internal short
o Poorly controlled
welding process - Burr
height 80 µm in some
cases
o Normal swelling and
contraction occurs
during charge-
discharge cycling

12
 Manufacturer B Root Cause
o Some batteries were missing the insulation tape!!
o Samsung blames the flaws on its factories trying to get production started too
quickly to counteract lost sales.
o There are simply no short cuts when it comes to lithium ion battery
manufacturing process control

13
 LITHIUM ION BATTERY
FAILURE MODES AND
MECHANISMS

14
14
 LITHIUM ION BATTERY FAILURE MODES
Lithium Ion Battery Failures

Non-energetic Energetic Failures

Failures

Capacity Electrolyte
Loss leakage
IR Cell Fire Venting
Increase swelling
Permanent
Safety Feature Explosion
Enabled

15
 BENIGN, ENERGETIC AND NON-ENERGETIC

o All non-energetic failures are not benign

o What dictates whether a failure is energetic or not?

o Same initiating fault can have different outcomes

o Depends on whether the initiating fault can create a self-

sustaining exothermic reaction

16
 LITHIUM ION BATTERY FAILURE CAUSE
Mitigation Cause Outcome
Metallic Contamination/Burrs/weld
Non-
defects
energetic
Manufacturing Mechanical
Lithium Plating Heat Failures
quality and damage
process control Dissipated>
Low Heat
Anode/cathode
Generated
ratio
Low electrolyte
Design Anode delam
Internal short
Elevated Cell
circuit
Low temp
Temperature
charging
External short circuit
Safety
electronics High ambient temp Heat
and cell Dissipated<
internal Overcharge Heat
safety Generated
Overdischarge Thermal
features
runaway

17
 CELL REACTIONS AT ELEVATED TEMP -1
o Breakdown of passivating SEI layer on anode
o Excessive currents, overcharging, or high external ambient temp
o Starts at 80 C. New SEI formed but at a higher uncontrolled rate in an
exothermic reaction. Self accelerating reaction
o Electrolyte breakdown
o Organics in the electrolyte break down releasing flammable hydrocarbon
gases but no oxygen.
o Typically around 110 -120 C
o Pressure starts to build up. Even
if temp rises above flash point
no burning due to lack of oxygen

18
 CELL REACTIONS AT ELEVATED TEMP -2
o Safety vent pops to prevent explosion (18650 metal can type) – now have
oxygen available
o Separator melting occurs around 155 C, causing electrodes to short
o Further temperature rise causes metal oxide breakdown at cathode releasing
oxygen in an exothermic reaction. For Cobalt oxide this happens at 200 C
o Highly flammable organics, elevated temp, and oxygen

19
 ELEVATED TEMP AND FAILURES
o Elevated temperature and cell
failure are intricately tied
together
o Elevated temperature negatively
impacts capacity
o At higher rates, higher capacity
degradation
o 50% Loss in cycle life from 1 C to 1.2
C charging rate
o Cannot be explained by temperature Choi, S. S., & Lim, H. S. (2002). Factors that affect cycle-life and
possible degradation mechanisms of a Li-ion cell based on LiCoO2.
rise alone Journal of Power Sources, 111(1), 130-136.

20
 LITHIUM PLATING – WHY IS IT BAD?
o Rapid performance degradation (sudden
death) – lithium plating is highly reactive
to electrolyte
o electrolyte and lithium consumption
causing electrode dry out
o further lowering of anode to cathode
ratio
o increased impedance and further risk of Image source : Safety of Lithium-Ion Batteries,
plating Zhang et al; Lithium-Ion Batteries
Advances and Applications
2014, Pages 409–435
o Safety issues – risk of dendritic growth;
exothermic reaction between plated lithium
and electrolyte
21
 LITHIUM PLATING
o When does it happen?
o Operation outside specification window- overcharging, high charging rate, low temperature (protection circuitry)
o Battery/application design – low anode/cathode, low electrolyte, mechanical deformation from product (design
engineering/quality)
o Manufacturing defects – eg anode delamination, mechanical deformation, poor quality cells (quality
engineering)

Image Source: Understanding

undesirable anode lithium
plating issues in lithium-ion
batteries, Liu et al, RSC Adv.,
2016,6,

22
 LITHIUM ION SAFETY
Abuse Manufacturing Cell & Application Handling
Defects Design
Storage
Causes
Failure

Thermal Abuse
Internal Shorts Cell Design
Electrical Abuse
Assembly into host
Application design device
Mechanical Abuse User
Mitigation/

• Quality, Process • Design reviews • Process and

• BMS & Circuitry
Val.

Control • CT Scans/App procedure review

• Standardized Tests
• CT scans/Manuf audit specific testing • Self discharge tests
Field Failure
%

2% 90% 5% 3%
Near Miss
Events

0% 50% 25% 25%

23
 Internal Shorts – ‘Soft underbelly’
Internal shorts are typically the result of manufacturing defects
and are not effectively mitigated by safety systems

There is no good internal short circuit test that effectively screens

out these defects

The best defense is to have sound manufacturing process controls

24
24
 Improper BMS Design
o Poorly designed BMS and use of improper chargers are
responsible for some of the spectacular field failures
o Over-voltage failures are more spectacular and immediate than grown
in manufacturing defects which can take time to manifest themselves
o Battery protection system includes the charger circuitry,
protection circuit module located at the battery, and is
optimized for a specific cell chemistry and application
o Good BMS design should include use of a custom connector so that
everyday USB chargers can’t be plugged in and allowed to abuse the
cell

25
 LITHIUM ION CELL
MANUFACTURING
PROCESS

26
26
 MANUFACTURING CONTROLS

o Incoming raw materials

o Electrode fabrication and cell assembly

o Environmental control

27
 POWER DENSITY VS ENERGY DENSITY
o Energy density
o Pack as much active material as possible
o Minimize fines which make wetting difficult and require more
solvent and lower the solids content in slurry
o Power density
o Higher void volumes, lower
electrode pressed density and
thickness

28
 MANUFACTURING INCOMING RAW MATERIALS
o Incoming powders – Tap density, particle size distribution
(PSD), surface area, purity
o Binders and binder solvents
o Separator
o Electrolyte
o Current collectors
o Dry room storage (dew point of at least -40 C) . Dew point is
used to express water vapor concentration at this level because
the corresponding relative humidity value is less than 1%.

29
 ELECTRODE FABRICATION

QC – electrode
QC -Viscosity and QC –thickness, slurry QC – thickness, thickness once/hr,
dispersion control metering adhesion QC –burr control;
roller gap check 4-6
Risk– shorts, Risk– non-uniform Risk– blisters, lack of tension control, cutting
hrs, porosity. Risk–
unreacted lumps coating leading to adhesion leading to wheel maintenance.
lack of cell
cause risk of dryout shorting risk, dryout lithium plating Risk–internal shorts
performance for
and plating energy or power

30
 CELL ASSEMBLY, FORMATION AND TESTING

Winding/Stacking
QC – Weight before and QC – OCV, IR, weight,
QC –alignment
after; stringent moisture dimension check prior to
Risk–internal shorts QC – OCV, IR, weight,
control formation. Rest to allow
Tab welding dimension, followed by
Risk – electrode dryout and electrolyte wetting after
QC – burr/weld height aging qualification tests
plating; swelling from filling, followed by
control
moisture formation
Risk – internal shorts

Battery Manufacturing. (n.d.). Retrieved March 22, 2017, from http://w3.siemens.com/markets/global/en/battery-manufacturing/applications/process/pages/default.aspx

 DRYING TEMPERATURES
o The process involves a multi-zone oven with low
temperatures for the first zone, higher temperatures for the
middle zone, followed by a lower temperature for the final
zone.
o Specific temperatures will depend on binder chemistry and on
slurry properties.
o For PVDF binder on the cathode, the recommended drying oven
temperature profile for a 5-zone oven is as follows: zone 1 – 75-90
°C; zones 2-4 – 125-130 ° C; zone 5 –approximately 75 ° C. A 4-
zone oven should run at slower speed to allow more solvent
evaporation.
32
 GENERAL MANUFACTURING GUIDELINES
o Incoming materials control
o Internal specifications that identify, minimize and control all
known and likely impurities in incoming materials
o Internal specifications that control material properties or specs
o Ability to track changes in vendor materials

33
 GENERAL MANUFACTURING GUIDELINES
o Manufacturing process control
o Safety critical equipment must be identified - process of verifying
equipment operation periodically. Preventive maintenance plan
implementation
o Procedures to avoid metal contamination throughout the manufacturing
process
o Processes to collect loose material, such as coating dust
o A method of detecting mechanical damage to electrodes in the
manufacturing process, such as an automated vision system
o Statistical process control (SPC) to monitor maximum particle size,
slurry viscosities, coating weight, calendered thickness, weight of
electrolyte dispensed, cell weight, open circuit voltage (OCV) and
capacity
34
 ENVIRONMENTAL CONTROL
o Robust environmental control with a specific focus keeping ambient
moisture minimized
o Destabilizes SEI layer and electrolyte and causes gassing

35
 LITHIUM ION CELL
DESIGN GUIDELINES

36
36
 CELL DESIGN GUIDELINES
o Anode should overhang cathode by 0.5 mm or more on all sides for stacked
cell or along top and bottom ends for jellyroll (min of 0.1 mm per IEEE
1625/1725)
o Anode should have higher electrochemical capacity than cathode by 10-15%.

o Example 1 g anode, specific capacity is 350 mAh/g. So total anode

capacity is 350 mAh
o 1 g cathode , with specific capacity of 280 mAh/g has total capacity of 280
mAh
Cathode
Cathode shall never put out more lithium
Anode
ions than the anode can accommodate.
Separator

37
 CELL DESIGN GUIDELINES
o Separator overhangs anode on all sides (room temperature to at
least 110 C- IEEE 1625/1725)

o Less than 5% shrinkage in both machine and transverse

directions at 90 C as a minimum

o Separator should have sufficient mechanical

strength to withstand cell assembly operations. Cathode

Anode
Separator

38
 CELL DESIGN GUIDELINES
o Product design – make sure there is enough room for battery to
expand as it goes through charge –discharge cycles. Recommend 10
% margin.
o Pay particular attention to corners

o Poor manufacturing can reduce design margin

o Cutting operation variability
o Pick and place variability

39
 ARTICLE QUALITY
ASESSMENT : CELL CT
SCANS AND TEARDOWN

40
40
 ARTICLE QUALITY ASESSMENT – CT SCANS

o Deep discharged cell

41
 ARTICLE QUALITY ASESSMENT- CT SCANS
o Exercise - Describe what you see
o Electrode alignment is good on right image
o Variability in jellyroll winding on left and middle images
o Insufficient anode overlap in center of middle image

42
 PHYSICAL ARTICLE QUALITY ASESSMENT – CT SCANS
o Conduct CT scans and cell teardowns on a handful of units
o What to look for in CT scans
o Uniform cell winding or stacking
o No particulates
o No significant electrode delamination
o Anodes should overhang cathode by 0.5 mm ideally but a
minimum of 0.1 mm on each side
o No excessive deformation at pouch corners
o Cutting operation/pick and place variability

43
 ARTICLE QUALITY ASESSMENT – TEARDOWNS
o Look at a few electrode pieces using optical microscopy
and SEM/EDS

44
 LITHIUM ION INTERNAL
AND EXTERNAL
PROTECTION SYSTEMS

45
45
 CELL SAFETY PROTECTION MECHANISMS
o Positive Temperature Coefficient (PTC) device - inhibit high current
surges
o Charge interrupt device (CID)- opens the electrical path if an
excessively high charge voltage raises the internal cell pressure to a
threshold value
o Safety vent- allows a controlled release of gas in the event of a
rapid increase in cell pressure
o Hot electrolyte vapors and gas will always blow
towards the burst disc, instead of splitting the sides 

o Shutdown Separators

46
 PTC DEVICE
o PTC - doughnut shaped device that sits between two metal
plates and is made of a polymeric material.
o At high currents or temperatures, resistance of the PTC
increases sharply causing the current to drop.
o The PTC is resettable and reverts
back after the fault is removed.
o Once activated it subsequently
activates at a lower current and
temperature.
Image source: nasa.gov

47
 CHARGE INTERRUPT DEVICE
o Works by releasing the connection at the positive terminal, and
opening the electrical path
o Pressure valve which will disable the cell permanently of
pressure in the cell is too high
o Is not resettable

Image source: nasa.gov

48
 POUCH CELL PROTECTION
o Pouch cells do not have an internal CID, PTC or safety
vent

o Can have PTC or fuse elements in series with cell

Image source: nasa.gov

49
 SHUTDOWN SEPARATOR
o Separator is usually made of polyethylene (PE), polypropylene (PP) or a
combination of the two.

o Inner PE layer shuts down at 130°C by closing the pores, the outer PP layers do not
melt until reaching 155°C.
Image Source : Battery University

50
 SHUTDOWN CURVES
o Separator should increase its resistance by two orders of
magnitude at shutdown temperature (typically 130 C)

Image Source : Arora and Zhang, Battery Separators, Chem. Rev., 2004, 104 (10), pp 4419–4462

51
 SHUTDOWN SEPARATOR PROPERTIES
o Know separator properties
o Thickness
o single vs multiple layer (PE, PP or combination)
o ceramic coated or not
o Ceramic coatings can enhance thermal stability and prevent separator collapse till 200 C and
beyond
o Ceramic coated separators usually may not have the mechanical strength to withstand winding and
assembly- irrelevant for prismatic or stacked designs

Impedance (1 kHz AC) vs Shutdown temperature of electrolyte soaked separators : (a,b) Polyethylene and (c)
polypropylene

52
 BATTERY MANAGEMENT
SYSTEM (BMS) AND
PROTECTION CIRCUITRY

53
53
 Operating Outside Specifications
o Operating outside of specifications

Image source : Electropaedia

54
 Severity of Thermal Runaway
o Depends on a number of factors
o State of charge (SOC)
o Ambient temperature
o Cell chemistry
o Cell design
o Most severe thermal runaway occurs in an overcharged
state
o Case temperatures can reach 600 C.
o High temperatures are driven by exothermic reactions of the
electrodes and the electrolyte

55
 Thermal Runaway Initiation – Some Numbers
o Self heating temperature
o Fully charged 18650 cells brought to self heating temperature (70 to
90 C) in adiabatic environment go into thermal runaway in 2 days.
o Fully charged 18650 in adiabatic environment brought to 150 C
(with separator melting) will run away in minutes
o UL standard requires fully charged cells to withstand 4 hour storage
at 75 C, and 10 min storage at 130 C.
o IEEE standard requires 1 hour exposure at 130 C
o Overcharge
o Charging a 4.2 V system to 5 V will almost certainly cause
immediate thermal runaway

56
 EV Bus Failure
o EV electric bus caught fire in Shenzhen, China during
charging

o BMS Failure

o Without a BMS, there is no

safe lithium ion battery

57
 ELECTRONIC PROTECTION SYSTEMS
o Consist of charger and a battery protection printed circuit
board (PCB)
o Also called a battery protection circuit module (PCM)

o Important functions of protection systems include monitoring,

controlling and terminating charge and discharge as needed.

o Failure of protection circuitry to either sense or respond to an

out of range condition, causes battery failure

58
 BMS FUNCTIONS
o Maintain cells within operating window and prevent cells
from going into
o Over voltage
o Over current
o Over temperature
o Over discharge
o Balance individual cells to enhance overall capacity
o Disconnect batteries in a safe way in emergency situations
o Predict remaining capacity or state of charge
BMS Webinar : https://www.dfrsolutions.com/battery-management-systems-and-safety-and-reliability-webinar

59
 OVER CHARGE - VOLTAGE
o Most obvious failure mode is exceeding specified voltage
o Charging a 4.2 V system to 5 V will almost certainly cause immediate
thermal runaway
o Charging at excess currents

o Overcharge effects
o Anode – lithium plating rather than intercalation
o Cathode –excess de-intercalation causes crystal structure to collapse and
release heat
o Heat and gas release (both Joule heating and parasitic reactions)
o Electrolyte and electrode decomposition

60
 OVER VOLTAGE
o Over voltage may be applied to the battery from a defective
charger or due to improper monitoring on a single cell
o Slight overcharge (from minor deviations in voltage monitoring)
causes capacity loss rather than direct thermal runaway.

o Overvoltage protection can be implemented by opening a

charge MOSFET or a fuse

o Overcharge protection is so critical that multiple independent

circuits are typically used to prevent single points of failure

61
 OVER DISCHARGE
o Hazard from over discharge is highly
underestimated

o When a cell goes into deep discharge,

copper ions from the negative electrode
current collector dissolve. On recharge
copper dendrites can form.

o Over discharge can also cause breakdown of Image Source : Rui Guo,1 Languang
Lu,1 Minggao Ouyang,a,1 and Xuning

the SEI layer and gas formation. Feng1, Sci Rep. 2016;

62
 How Does a Battery Go
into Deep Discharge?

63
63
OVER DISCHARGE SCENARIOS

o Uncontrolled storage without appropriate recharge

procedures

o Mechanically damaged cells (from electronics

impinging on cell)

64
 Discharge During Storage
o Three kinds of discharge occur during storage
o PCM sleep current and leakage currents
o Battery self discharge
o Manufacturing quality

o Temp

o State of charge

o Device sleep currents

o At 3 V (or other threshold cutoff), load is disconnected although above
‘consumption currents’ are active.
o At deep discharge cutoff value, of 2 V (or other manufacturer specified
value) PCM and device sleep currents are turned off, but battery self
discharge continues.
65
 Battery Self Discharge
o Lithium ion self discharge around 1-2% per month + a
few % cent for PCM

o High SOC and temperatures degrade storage life (and

cycle life)
o Rule of thumb – 10 C increase in temperature doubles self
discharge rate

o Store at conditions close to 25 C and 40 % SOC

66
 PCM (BMS) Self Discharge
o To keep the contamination as low as possible to reduce
leakage current, de-ionized water wash should be used in
the board cleaning process
o Verify the board cleanliness to make sure the levels of
contamination is low
o Investigate if humidity is an issue and that conformal
needs to be used

67
Deep Discharge Checklist
o Have a pre-check charging function on batteries where deep
discharge cutoff voltage was reached. Charger circuit checks
if a deeply discharged battery is reaches a threshold value in
give time. Otherwise considered a ‘damaged’ battery
o Mitigating hazard from copper shunts
o Proper battery storage and recharge procedures
o Minimize PCM leakage currents
o Ensure cell quality
o Prevent cell mechanical damage

68
 OVER CURRENT PROTECTIONS
o Over current can cause
o Degradation in cycle life
o Thermal runaway
o Threshold limits for current are functions of both current and time.
Protection circuit system can use different combinations of time and
current to produce a fault. Example - high current/short time or
lower current/long time.
o Some faults are recoverable such as when a MOSFET is turned on,
and others are non-recoverable such as when a fuse is ignited.
o Causes of over-current could be a defective charger, or due to an
internal short.

69
 OVER CURRENT
o A good battery management system will limit charge current and voltage at high and
low temperature extremes per Japan Electronics and Information Technology Industries
Association (JEITA) guidelines.
Reduce charging Reduce charging
current and/or current and/or
voltage voltage

Cold Cool Warm Hot

(0 °C) (60 °C)

70
 SHORT CIRCUIT PROTECTION

o Current limits are incorporated into the protection

circuits located in pack or device

o Circuits monitor current in and out of battery and open up

MOSFET to interrupt current

o Backup protection usually includes a fuse or PTC

placed in series with battery pack
71
 BATTERY LIFE,
DEGRADATION AND
STORAGE

72
72
 BATTERY LIFE AND AGING ISSUES
o Battery life example
o Nominal capacity is 2900 mAh. End of life capacity at 80% of initial
capacity is 2300 mAh.
o Is this data sufficient to give you a life of 500 cycles?

73
 BATTERY LIFE DEGRADATION
o Calendar aging vs cycle life aging
o Insertion or ejection of the Lithium ions into and out of the intercalation
spaces during cycling causes the electrode materials to swell or contract.
o Repetitive cycling can weaken the electrode structure reducing its adhesion
to the current collector. This can lead to reduction in charge capacity.

74
 BATTERY LIFE DEGRADATION: CALENDAR AGING

o Storage degradation : high temperature aging causes

growth of the passivating layer

o It consumes lithium and electrolyte and leads to capacity loss

and impedance increase (both capacity and power fade).
Pores can be blocked as a result.
o Low rate batteries may not see a big impact (voltage
drop = IR)

75
 BATTERY LIFE DEGRADATION: CALENDAR AGING
o Have two distinct mechanisms
that impact cell life
o Battery aging tests should
involve high temperature
storage tests

Image source : Electropaedia

76
 REVERSIBLE VS IRREVERSIBLE STORAGE LOSS
o Characterize both reversible and irreversible storage loss
o In this example 25% irreversible and 5% reversible capacity
loss

Assume a = 2900 mAh a

d = 70% * a = 2030 mAh
e
e = 95% *a = 2700 mAh
d

77
 LITHIUM ION
CHEMISTRIES

78
78
 Battery Chemistry
o Term Lithium-Ion encompasses many different chemistries
o Anode – graphite (Lithium Titanate LTO for very fast charge cells)
o Cathode - Cathodes are lithiated metal oxides or lithiated metal
phosphates
o Lithium Cobalt Oxide (LCO)
o Lithium Iron Phosphate(LFP)
o Nickel Manganese Cobalt (NMC)
o Lithium Manganese Oxide(LMO)
o Cathode chemistry is where you get enhancements in safety,
energy and power density

79
 Battery Chemistry
o Lithium Cobalt Oxide (LCO) – commonly used in consumer electronics
o High energy density
o Low power
o Least safe
o Moderate cycle life
o Lithium Iron Phosphate(LFP) –– automotive, power tools,
UPS, e-cigs
o Safest chemistry
o High power density
o Very high cycle life
o Lower voltage/Lower energy density
o Higher self discharge rate

80
 Battery Chemistry
o Nickel Manganese Cobalt (NMC) –common in tools, EV applications,
e-cigs – usually 1/3 proportion, but customization is possible
o Can be optimized for power or energy
o Good safety
o Good cycle life
o Lithium Manganese Oxide(LiMn2O4) –– power
tools, EV and hybrid vehicles, e-cigs
o Low internal resistance/high power capability (from
Manganese)
o Good safety
o Lower energy – blends with NMC are used to
enhance energy
81
 Battery Chemistry Summary
o Knowing chemistry helps to map out worst case scenario
o For pouch cells look at MSDS
Chemistry LCO NMC LFP LMO
Nominal Voltage(V) 3.6-3.7 3.6-3.7 3.2-3.2 3.6-3.7
Charge Voltage(V) 4.2 4.2 3.5-3.6 4.2
Safety Poor Good Highest Good
Cycle Life >500 >500 >1000 >500
Peak Load current (Best 2C >30C >30C
result) (<1C) (<10 C) (<10 C)

Specific energy (Wh/Kg) 150-250 90-120 100-150

Thermal Runaway Temp (ºC) 150 210 >270

Used Since 1991 2003 1999 1996

Designation ICR INR IFR IMR

82
 Battery Chemistry in Current EV Systems
o Do not see the word LCO!

83
 ESTIMATING STORED
ENERGY

84
84
 BATTERY RISK ASESSMENT
o Risk assessment
o How much energy and wattage does the battery have?
o How fast is the energy released?
o Is the product worn on or close to the body?
o What is the chemistry?
o New product category : Are there specific user behaviors/product
design interactions that increase the risk and impact of thermal away?
o Risk mitigation
o Trust but verify
o Do not trust till you verify
o Map out the worst case

85
 STORED ENERGY
o Stored energy is a combination of electrical and chemical
energy
o Electrical Energy
o Chemical energy may be approximated by using heats of
combustion of various flammable components in cell.

86
 STORED ENERGY PRISMATIC EXAMPLE

o Specification :
o 3.7 V
o 2.96 Wh
o 800 mAh
o Useful information : 1 Wh = 3.6 kJ
o Total stored energy = 2.96 * 3.6 = 10.65 kJ

87
 STORED CHEMICAL ENERGY: SMALL PRISMATIC
o Assume 1 to 5 g of electrolyte for small prismatic or pouch cell.
Assume 0.5 to 1 g of separator.
o Electrolyte solvents are generally organic carbonates, such as diethyl
carbonate (DEC) , ethylene carbonate, dimethyl carbonate, and
ethylmethyl carbonate.
o Using the heat of combustion of DEC at 20.92 kJ/g, 21 to 105 kJ of energy from
electrolyte combustion
o Separator is made of polyethylene, polypropylene or combination of
the two.
o By using polypropylene heat of combustion as an approximation at 42.66 kJ/g,
21 to 42 kJ energy for the separator
o Total chemical energy approximation is 42 to 147 kJ

88
 STORED ENERGY : SMALL PRISMATIC
o Estimate of total energy released is 52 to 117 kJ

Cell Type Energy Low (kJ) High (kJ) Amount (g)

Chemical Energy Combustible 42 147
materials Total
Separator 21 42 0.5 to 1
Electrolyte 21 105 1 to 5
Electrical (nominal voltage to 10.65 12.1
fully charged state)
Prismatic Total 52.65 117

89
 STORED ENERGY 18650 EXAMPLE SOLUTION
o Specification :
o 3.7 V
o 9.62 Wh
o 2600 mAh
o Useful information : 1 Wh = 3.6 kJ
o Heat of combustion of DEC = 20.92 kJ/g
o Polypropylene heat of combustion = 42.66 kJ/g
o For comparison a 190 g stick of dynamite can release 1 MJ of energy 1.
Cell Type Energy Low (kJ) High (kJ) Amount (g)

Chemical Energy Combustible materials Total 122 235.61

Separator 59.72 68.25 1.4 to 1.6

Electrolyte 62.36 167.36 3 to 8

Electrical (nominal voltage to fully charged 34.62 39.3

state)
18650 Total 157 207

1. https://en.wikipedia.org/wiki/Dynamite
90
 Is the 18650 Hazard
Relevant to You?

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 Small Batteries
o Smaller batteries - 20 mAh to 500 mAh
o Energy released is 10- to 100 times lower than the 18650
o Smaller capacity batteries release smaller amounts of energy

o 150 -200 mAh batteries generally used for headphone applications such as in
illustration
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 Worst Case Analysis
o Calculate total energy released from your cell
o Electrical energy + chemical energy
o Use thermal analysis to estimate temperature rise and
compare against allowable surface temperatures/standards
Material Burn Threshold for
contact of 0.5 s (ºC)
Bare metal 67-73
Ceramics, glass and stone 84-90
Plastics 91-99
Wood 128-155

European standard BS EN 13202:2000

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 Skin Burn Temperatures
o Potential for burn hazard may be estimated
Effect Description Skin
Temperature
(ºC)
Pain Tingling hot sensation 44
1st degree burn Superficial injury to outer layer; skin 44-55
is reddened; painful
2nd degree burn Outer layer is burned through; 55-60
second layer damaged; skin is moist
and reddened with blisters; intense
pain
3rd degree burn All skin layers are damaged 60

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 VENT GAS RISK

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 Vent Gas Flammability
o Vent gases mainly consist of H2, hydrocarbons (also called THC or
total hydrocarbon concentration in figure below), CO2 and CO.
o Flammable gases include H2, CO and hydrocarbons

Ref 1. US DOT/FAA Study,

Lithium Battery Thermal
Runaway Vent Gas Analysis , Nov
2016

Major gas species concentration for18650 LiCoO2 cell

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 Ignition Risk
o When a lithium ion battery vents, the gas mixture will mix with surrounding air
and may or may not ignite

o The following conditions have to be met for an ignition event

o Air fuel mixture is within the Lower Flammability Limit (LFL) and (Upper Flammability
Limit) UFL limits
o Ignition source is present

o The most dangerous materials are those with the lowest flash point and widest
flammable ranges.

o A hot cell case or hot metal sparks ejected from the cell could create an ignition
event, if the mixture is within flammability limits.

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 CHEMICAL SPILL RISK

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 Chemical Spill Risk
o In the absence of a fire, potential hazard from a damaged lithium ion
battery includes the following:

o Release of a electrolyte containing a corrosive salt. Electrolyte is extremely

corrosive and may cause permanent blindness. If ingested through the
mouth, liver and kidney damage is possible.

o Reaction of the electrolyte with water/humidity may generate hydrofluoric

acid which are highly toxic and corrosive to the eyes, nose, throat and skin.

o Release of volatile organics, toxic gases such as CO, HF.

Ref . Various MSDS sheets

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 Chemical Risk – Lithium Ion and Primary Lithium
o Lithiated carbon in a charged anode, the Solid Electrolyte
Interphase (SEI) layer or any free lithium
(dendrites/plating) will burst into flames when exposed to
moist air

o Reaction of lithium with water produces H2 in an

exothermic reaction.
o Significant heat is released in this reaction, and this can ignite the
H2.

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 Lithium Ion Life Cycle –
Cradle to Grave

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 LITHIUM ION BATTERY LIFE CYCLE
o Cell Manufacturing
o brought to a low to moderate state of charge for shipping/storage
o Transportation
o Warehouse storage
o Pack or device assembly
o OEM device shipment
o Device Usage
o Recycling

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 Transportation Procedures
o Almost all failures are related to improper packaging (potential
for mechanical damage and external shorts) and shipment
procedures.

o International Air Transportation Association (IATA) shipment

procedures for dangerous goods. Cell manufacturers must show
proof of UN 38.3 certification
o 1) Lithium ion batteries (not contained in equipment) shall not be shipped
with SOC greater than 30 %.
o 2) Shall pass UN 38.3 battery of tests
o 3) Shall not be shipped on passenger aircraft
See http://www.iata.org/whatwedo/cargo/dgr/Documents/lithium-battery-shipping-guidelines.pdf

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 Transportation Procedures
o Small cell shipment exceptions to class 9 dangerous goods classification
o Only Carry-on and Section II are exempt from Class 9 hazardous material
designation.

Image source :
Battery university

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 Storage and Warehouse Handling
o Have procedures in place for safe handling of lithium ion
batteries
o Protection from short circuit, high temperature is critical
o Pouch cells must use recessed packaging trays

105
 Lithium Ion Recycling Procedures
o Do not single stream recycle lithium ion batteries
o High risk of ignition with surrounding paper and cardboard
o Lithium Ion batteries can be recycled, but only at specified
locations. Visit https://www.call2recycle.org/locator/
(Rechargeable Battery Recycling Corporation)
o 86% of US and Canadian residents live within 10 miles of
drop-off location
o https://www.call2recycle.org for battery recycling resources

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 Lithium Ion Recycling Procedures
o Do not discard as trash
o When collecting batteries, make sure they are taped or
insulated
o Recommend drop-off instead

107
 COMPLIANCE TESTING

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 BATTERY COMPLIANCE TESTING
o Tests that have the same name under different standards
are not always the same.

o There are differences in terms of the state of charge,

aging of the cells and sample sizes and these can have
significant differences.

o The vendor must state the test standard, specify a test

description in addition to the name of the test.
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 BATTERY COMPLIANCE TESTING
o UN/DOT 38.3. Covers transportation safety testing for all lithium
metal and lithium ion cells and batteries. This is mandatory.

o UL safety standards
o UL 1642 – This standard is used for testing lithium cells. Battery level tests
are covered by UL 2054.
o UL 2054 (Household and Commercial Batteries) – For lithium batteries, UL
2054 defers all component cell level testing to UL 1642.

o CEI/IEC 62133 – this standard is voluntary in the US, but some

countries specify this standard.

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 BATTERY COMPLIANCE TESTING
o IEEE 1625/1725 – These standards are applicable to rechargeable batteries
for Multi-cell mobile computing devices and for Cellular phones respectively
(CTIA or Wireless Association).

o These standards take the most comprehensive approach to battery testing,

and emphasize that battery pack safety is a function of a) the individual cells
b) the battery pack, c) the host device, d) power supply accessories e) the
user f) the environment.

o Both standards require design analysis tools such as FMEA or fault tree
analysis. They also encompass industry best practices in manufacturing, and
in the areas of cell, pack, system, and charging accessory design.

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 Parting Thought

The more you know the

better!

112
Questions?
• Contact Vidyu Challa,
vchalla@dfrsolutions.com,
301-640-5834

• www.dfrsolutions.com resources page for

battery and other electronic reliability
resources
 APPENDIX

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 Battery Seal Quality
o Moisture ingress through
o Laminate face (extremely low due to metal barrier)
o Interfaces (no metal barrier)
o Terminals (good sealing practices mandatory)
o Compensate through large seal width ( generally 2 mm
min)
o Seal width checks

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 FLASH POINTS
o Flash points for common components of lithium ion battery
electrolytes are below.
Electrolyte Component Boiling Point Flash Point
Propylene carbonate (PC) 242°C 135°C
468°F 275°F
Ethylene carbonate (EC) 248°C 145°C
478°F 293°F
Di-Methyl carbonate (DMC) 91°C 18°C
195°F 64°F
Diethyl carbonate (DEC) 126°C 25°C
259°F 77°F
Ref . CRC handbook
Ethyl methyl carbonate (EMC) 107°C 25°C
of chemistry and
physics.
225°F 77°F

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 o Flammability limits for vent gases from Li Ion batteries are
in table below
Compound Lower flammability limit Upper flammability limit
(fuel volume %) (fuel volume %)
Hydrogen 4.0 75.0
Carbon monoxide 12.5 74.0
Methane 5.3 15.0
Ethylene 3.1 32.0
Ethane 3.0 12.5
Propylene 2.4 10.3
C4 hydrocarbons ~ 1.6-1.9 ~ 8.4 – 9.7
C5 hydrocarbons ~ 1.4-1.5 ~ 7.5 – 8.7

Ref . Combustion, Flames and Explosion of Gases , 2 nd Edition, Academic Press, NY 1961

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