Why Lithium Ion Batteries Fail

Vidyu Challa
• It is easy to make a battery that works, but hard to
make a battery that does not fail
• Battery performance is very closely tied to the
manufacturing process and how stringent the
quality controls are.
• Making batteries in a university lab/startup, is entirely
different matter from making them at scale.
• Large corporations are not immune either.
• Recent high profile battery incidents mostly
stemming from inadequate process controls in the
manufacturing process.
Outline
• Battery working mechanism
• Root cause analysis of Samsung battery failures
• Battery failure causes
• Temperature
• Lithium Plating
• Internal shorts
• Mitigation methods
• Design
• Manufacturing
Lithium ion battery working mechanism
• Anode negative electrode, cathode positive electrode
• Lithium ion is an intercalation battery (‘rocking chair mechanism’)
• Solid electrolyte interphase (SEI) formed during first few charging cycles
• SEI can be unstable outside operating window
Samsung Galaxy Failures
• Galaxy Note 7 fires were reported within a few weeks of the
product launch.
• Samsung recalled affected phones, and pointed to a
manufacturing error from its battery supplier Samsung SDI.
• The batteries were swapped with ones from its Chinese
supplier ATL.
• Replacement phones that were supposed to be “fixed” also
started to catch on fire.
• Samsung scrapped the entire product line. 2.5 million phone
recalls prior.
Source : Information in public domain
• Flattened jellyroll structure

Source : Samsung Galaxy Note 7 failure investigation press conference, Jan 2017
 Manufacturer A Root Cause
• Damage to the negative electrode windings caused by
deflection by a pouch design that did not provide sufficient
volume to accommodate the electrode assembly.
• Curvature of pouch causes deflection of the negative
electrodes.

Source : Samsung Galaxy Note 7 failure investigation press conference, Jan 2017
Manufacturer A Root Cause
• Negative electrode damage provides multiple pathways to
cell internal short circuit and thermal runaway under normal
cycling conditions
• Damage to the separator
• Lithium plating

Source : Samsung Galaxy Note 7 failure

investigation press conference, Jan 2017 .
Images courtesy Exponent
Overcrowded school bus
• Internal short due to cathode Manufacturer B
tab welding defects
(abnormally high burrs) and the
copper foil of the anode directly
opposite the defective welds.
• Poorly controlled welding of the
positive tab created sharp
features. Height of burrs was
80 µm in some cases.
• Normal swelling and
contraction that occurs
charge-discharge cycling
forced weld defects to
penetrate the
separator/insulation tape. Source : Samsung Galaxy Note 7 failure investigation press
conference, Jan 2017
• Some batteries were missing the insulation tape!!
• Samsung blames the flaws on its factories trying to get
production started too quickly to counteract lost sales.
• There are simply no short cuts when it comes to
manufacturing process control

Source : Samsung Galaxy Note 7 failure investigation press conference, Jan 2017
Why did these batteries fail after passing
standards based tests?
• Majority of standards based testing is focused on abuse
tolerance – overcharge, crush, impact and external short
circuit
• Majority of field failures
• under normal operating conditions
• occur at ppm levels
• Sony 2006 failures – 1 in 200 K (triggered 10 million recalls)
• are due to manufacturing defects
• are not mitigated by battery safety systems because they
are from internal shorts
• lithium plating is implicated in many of these failures
 Lithium Ion Battery Failures

Non-energetic Energetic Failures

Failures

Capacity Electrolyte
Loss leakage
IR Cell
Increase swelling Fire Venting
Permanent
Safety Feature
Explosion
Enabled
Mitigation Cause Outcome
Metallic
Contamination/Burrs/weld defects Benign
Manufacturing
Mechanical Failures
quality and Heat
damage Lithium Plating
process Dissipated>
control Low Heat
Anode/cathode
ratio
Generated
Design Low electrolyte
Anode delam Internal short
circuit Elevated Cell
Low temp Temperature
charging
External short circuit
Safety
electronics High ambient temp Heat
and cell Dissipated<
internal Overcharge Heat
safety Overdischarge Generated Thermal
features runaway
• Battery working mechanism
• Recent Samsung battery failures
• Battery failure causes
• Elevated Temperature
• Lithium Plating
• Internal shorts
• Mitigation methods
• Design
• Manufacturing
Cell Reactions at Elevated Temperature
• Breakdown of passivating SEI layer on anode
• Excessive currents, overcharging, or high external ambient temp
• Starts at 80 C. New SEI formed but at a higher uncontrolled
temperature in an exothermic reaction. Self accelerating reaction
• Electrolyte breakdown
• Organics in the electrolyte break down releasing flammable
hydrocarbon gases but no oxygen.
• Typically around 110 -120 C
• Pressure starts to build up. Even if temp rises above flash point no
burning due to lack of oxygen
• Anodic reactions are the rate
limiting step
• Safety vent pops to prevent explosion – now have oxygen
available
• Separator melting occurs around 155 C, causing electrodes
to short
• Further temperature rise causes metal oxide breakdown at
cathode releasing oxygen in an exothermic reaction. For
Cobalt oxide this happens at 200 C
• Highly flammable organics, elevated temp, and oxygen
Lithium Plating
• When does it happen?
• Operation outside specification window- overcharging, high charging
rate, low temperature
• Battery design – low anode to cathode ratio, low electrolyte
• Manufacturing defects – eg anode delamination

Image: Understanding undesirable anode lithium plating issues in lithium-ion batteries, Liu et al, RSC Adv., 2016,6, 88683-88700
Lithium Plating
• Why is it bad?
• Rapid performance degradation (sudden death) – lithium plating is
highly reactive to electrolyte
• electrolyte and lithium consumption causing electrode dry out
• further lowering of anode to cathode ratio
• increased impedance and further risk of plating
• Safety issues – risk of dendritic growth; exothermic reaction
between plated lithium and electrolyte

Image source : Safety of Lithium-Ion Batteries,

Zhang et al; Lithium-Ion Batteries
Advances and Applications
2014, Pages 409–435
Do all internal shorts cause thermal runaway?
• Risk of thermal runaway depends on resistance of short, location, and
cell state of charge
• Anode to cathode shorts are usually low power, and pose low risk for
thermal runaway
• Anode to Al current collector are high power, and also involve a
chemical reaction at the anode (rate limiting step). High risk for thermal
runaway especially in charged state
Cu current collector Al-Anode Al-Cu

Graphite Anode
Anode-cathode
Separator
Cu-cathode
Metal oxide Cathode
Al current collector
• Battery working mechanism
• Recent Samsung battery failures
• Battery failure causes
• Temperature
• Lithium Plating
• Internal shorts
• Mitigation methods
• Design
• Manufacturing
Design
• Anode should overhang cathode by 1-2 mm on all sides.
• Anode should have higher electrochemical capacity than cathode by 10-
15%.
• Separator overhangs anode on all sides
• Separator should have sufficient mechanical strength to withstand cell
assembly operations.
• Separator should increase its resistance by two orders of magnitude at
shutdown temperature (typically 130 C).

Cathode

Anode
Image source- Battery University Separator
 Manufacturing – Incoming raw materials
• Incoming powders – Tap density, PSD, surface area, purity
• Conductive additives
• Binders and binder solvents
• Separator
• Electrolyte
• Current collectors
• Dry room storage (dew point -40 to -50 C) . Dew point is used to express
water vapor concentration at this level because the corresponding relative humidity
value is less than 1%.

Cathode electrode components

Image source :Knoops et al, Journal of Vacuum Science & Technology A Vacuum Surfaces and
Films 30(1):010801-010801-10 · January 2012
 Sony 2006 recalls
• Electrode fabrication Boeing 2013 failures
metallic contamination
Source : information in public domain

QC -Viscosity and QC –thickness, slurry QC – thickness,

dispersion control metering QC – thickness,
adhesion
Risk– non-uniform porosity
Risk– shorts, Risk– blisters, lack QC –burr control
coating leading to Risk–lack of cell
unreacted lumps of adhesion leading Risk–internal shorts
cause risk of dryout shorting risk, dryout performance for
to lithium plating
and plating energy or power

Battery Manufacturing. (n.d.). Retrieved March 22, 2017, from

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

• Cell Assembly http://w3.siemens.com/markets/global/en/battery-

manufacturing/applications/process/pages/default.aspx

• Semb
• ly, Formation and Testing

Winding/Stacking
QC –alignment QC – Weight before and QC – OCV, IR, weight,
Risk–internal shorts after; stringent moisture dimension check prior to QC – OCV, IR, weight,
Tab welding control formation. Rest to allow dimension, followed by
QC – burr/weld height Risk – electrode dryout electrolyte wetting, aging qualification tests
control and plating followed by formation
Risk – internal shorts
Samsung 2016 recalls – tab welding defect
A123 2012 recalls – automated tab welding equipment miscalibration led to misalignment
Source : information in public domain
General Manufacturing Guidelines
• Incoming materials control
• Internal specifications that identify, minimize and control all known and likely
impurities in incoming materials
• Manufacturing process control
• An established process of verifying critical equipment operation periodically.
Preventive maintenance plan implementation
• Procedures to avoid metal contamination throughout the manufacturing process
• Processes to collect loose material, such as coating dust
• A method of detecting mechanical damage to electrodes in the manufacturing
process, such as an automated vision system
• Statistical process control (SPC) to monitor maximum particle size, slurry viscosities,
coating thickness and weight, dried coating per unit area, calendered thickness,
weight of electrolyte dispensed, cell weight, open circuit voltage (OCV) and capacity
• Robust environmental control with a specific focus keeping ambient
moisture minimized
How to be proactive with Li Ion Safety and
Reliability
• Robust design
• Stringent control of incoming raw materials and
manufacturing processes
• Standards based testing
• abuse tolerance
• CTIA is the most comprehensive and considers design,
manufacturing and system level effects
• Application specific testing
• System level interaction and tolerances (aging effects)
• User education – user is the last line of defense
Questions?