INTRODUCTION - ROBIN FOSTER

• Battery Solutions Lead at HSSMI

• Meng Chemical Engineering at Heriot

Watt University

• 5 Years in Lithium Ion Cell

Manufacturing

• 3 Years with HSSMI supporting Cell

and Battery manufacturing and
circular economy approaches to
electrification

2
HSSMI – Our work across the battery value chain
Lithium Ion Cell Fundamentals
ROBIN.FOSTER@HSSMI.ORG
 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?
 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?
What makes an Electrochemical Cell?

https://cdn0.woolworths.media/content/wowproductimages/large/259514.jpg
https://images-na.ssl-images-amazon.com/images/I/61IlGLOfrrL._SL1001_.jpg
https://www.bullionbypost.co.uk/media/cache/99/ca/99ca642dab4761e74c2f40d41eaf6ca4.j
https://upload.wikimedia.org/wikipedia/commons/1/1c/5mm_Super_Bright_Blue_LED.jpg
What makes an Electrochemical Cell?

https://www.howitworksdaily.com/british-science-week-heroes-of-science-issac-newton/
What makes an Electrochemical Cell?
What makes an Electrochemical Cell?
Primary Cells
Charged
Primary Cells e- → e- →
Discharging
Primary Cells
Discharged
Secondary Cells
Discharged
Secondary Cells e- → e- →
Charging
Secondary Cells
Charged
Secondary Cells e- e-
Discharging
Secondary Cells
Discharged
 Secondary Cells

Aluminium Foil

Active Material

Separator

Active Material

Copper Foil
Cell Formats

Prismatic Cell Cylindrical Cell Pouch Cell

https://www.alibaba.com/showroom/prismatic-cell-battery.html
https://www.vapecrew.co.nz/shop/accessories/batterieschargers/samsung-40t-
21700-4000mah-battery/
https://www.continuumpowerllc.com/cell-design/
Secondary Cells
• Casing
• Electrodes
▪ Anode
▪ Cathode
• Separator
• Electrolyte
• Tabs
Secondary Cells
Why Lithium?
Why Lithium?
Chemistry Abbreviation Voltage Cycles Discharge Cost Thermal Specific Energy
C-Rate Runaway (Wh/kg)

Lithium Cobalt
Oxide LCO 3.6V 500-1000 1C Mid/High 150ºC 150-200

Lithium
Manganese 1C Mid/High
LMO 3.8V 300-700 250ºC 100-150
Oxide (3C)

Lithium Nickel
Manganese
Cobalt Oxide NMC 3.7V 1000-2000 1C Mid/High 210ºC 15-220

Lithium Iron
Phosphate LFP 3.2V 1000-2000 1C (25C) Mid/High 270ºC 90-120

Lithium Nickel
Cobalt
Aluminium NCA 3.6V 500 1C Mid 150ºC 200-260
Oxide
 Pouch Cells
Cylindrical Cells
Prismatic Cells

Fiat 500e 2013 Ford Focus EV 2012 Tesla S 2012

LMO- LMO- NCA

NMC NMC

BMW i3 2014 Chevrolet Bolt 2016 Tesla X 2015

LMO-
NMC- NMC NCA
NCA

VW e-Golf 2016 Renault ZOE 2017 Tesla 3 2017

LMO-
NMC- NMC NCA
NCA
What Next?
 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?
 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?
How Cells Are Made

http://www.mdpi.com/1996-1073/9/2/104/htm
How Cells Are Made - Mixing
● Anode
● - Binder
● - Graphite

● Cathode
● - Binder
● - Lithium metal Oxides
● - Conductive additive
How Cells Are Made – Coating, Drying and
Calendering

https://www.targray.com/li-ion-
battery/coated-electrodes
How Cells Are Made - Slitting

https://www.zsw-bw.de/en/research/batteries/topics/production-and-process-research.html
How Cells Are Made – Winding, Assembly and
Filling

Separator – Anode
Separator - Cathode

http://www.mtixtl.com/Semi-AutomaticWindingMachineforElectrodesofCylinderCell-MSK-112A-Cylinder.aspx
https://www.youtube.com/watch?v=YPyJNk4p-TA
How Cells Are Made – Stacking, Assembly and
Filling

https://www.youtube.com/watch?v=vlYqabIqkmw
How Cells Are Made – Formation/Testing
How Cells Are Made
● 7 Key Stages of Cell Manufacture
How Cells Are Made
● 7 Key Stages of Cell Manufacture

1. Mixing
2. Coating/Drying
3. Calendering
4. Slitting/Cutting
5. Winding/ Stacking
6. Assembly/Filling
7. Formation
 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?
 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?
The Perfect Cell
Power on
Small
Demand

Long Fast
Lasting Charging
 The Perfect Cell

○ https://commons.wikimedia.org/wiki/File:Power_ vs_ energy_ density_ 3.svg

Two Extremes

High Power Cells High Capacity Cells

High Power Cells
• 30C to 40C Spikes

• Chemical vs Physical
Limiting Reaction

• Chemical Limiting
Reaction for Fastest
Reaction
 Aluminium Foil

Active Material
High Power Cells

Separator

Active Material

Copper Foil
Aluminium Foil
High Power Cells

Active Material

Separator

Active Material

Copper Foil
 High Power Cells

Aluminium Foil

Active Material

Separator

Active Material

Copper Foil
 High Power Cells

Aluminium Foil

Active Material

Separator

Active Material

Copper Foil
 High Power Cells

Aluminium Foil

Active Material

Separator

Active Material

Copper Foil
 High Power Cells

Aluminium Foil

Active Material
Separator

Active Material

Copper Foil
Aluminium Foil
Active Material
Separator Active Material
Copper Foil
High Power Cells
Aluminium Foil
Active Material
Separator Active Material
Copper Foil
High Power Cells
Aluminium Foil
Active Material
Separator Active Material
Copper Foil
High Power Cells
High Power Cells
High Power Cells
 -VE
High Power Cells

+VE
High Power Cells
• Design Considerations

• Auxiliary Components must take currents

• Ensure good connections

• Safety Devices – Protection Circuits, Venting

• Cooling System

• Capacity – (Fast Charge) Drill, Start/Stop Battery

Aluminium Foil
Active Material Separator

Active Material
HIGH POWER CELL

Copper Foil
High Capacity Cells
HIGH CAPACITY CELL
Aluminium Foil
Active Material Separator

Active Material
HIGH POWER CELL

Copper Foil
High Capacity Cells
HIGH CAPACITY CELL
HIGH CAPACITY CELL

HIGH POWER CELL

High Capacity Cells
• Design Considerations

• Control System – Limit high and spike loads

• Cell Life
• Deep/Shallow Discharge

• Cooling system – Tab Cooling less Effective

Summary
Design Aspects Performance Design Aspects Performance

Thick Current 30C to 40C Thin Current 2C to 3C

Collector Collector
Thin Electrode Short Life Thick Electrode Long Life
Coating Coating
Small Active Pulsed High Loads Larger Active Continuous low to
Material Particles Material Particles medium Loads
Summary
Design Aspects Performance Design Aspects Performance

Thick Current 30C to 40C Thin Current 2C to 3C

Collector Collector
Thin Electrode Short Life Thick Electrode Long Life
Coating Coating
Small Active Pulsed High Loads Larger Active Continuous low to
Material Particles Material Particles medium Loads

High Power Cell High Capacity Cell

High Power Cells

High Capacity Cells

 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?
 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?
Lithium Cells are Dangerous, Right?
Lithium Ion Cells – Just a Little Fussy

https://www.mpoweruk.com/lithium_failures.htm
Lithium Ion Cells – Just a Little Fussy

● Operational Effects: ● Non Uniformities

● - Voltage Effects ● - Manufacturing Defects
● - Temperature Effects ● - Abuse
● - Operational Fatigue
Voltage Effects – Over Voltage
SOC Safe Working Range

4.2V
Cell Voltage (V)

2V

0V
0 10 20 30 40 50 60 70 80 90 100

State of Charge
(%)
Voltage Effects – Over Voltage
4.2V
Cell Voltage (V)

2V

0V
0 10 20 30 40 50 60 70 80 90 100

State of Charge
(%)
Voltage Effects – Over Voltage
Discharged
Voltage Effects – Over Voltage
Charging
e- → e- →
Voltage Effects – Over Voltage
Charged
e- → e- →
Voltage Effects – Over Voltage
Overcharge
e- → e- →
Voltage Effects – Over Voltage
Overcharge
e- → e- →
Voltage Effects – Over Voltage
Overcharge
Voltage Effects – Over Voltage
- Lithium Plating

- Accumulate on Carbon Anode as Lithium Metal

- Reduction in free Lithium Ions – Capacity Reduced

- Non-homogenous build up → Dendrites → Short circuit

- Overheating

- Excessive Current → Increased Joule Heating → Temperature Increase

Voltage Effects – Under Voltage
SOC Safe Working Range

4.2V
Cell Voltage (V)

2V

0V
0 10 20 30 40 50 60 70 80 90 100

State of Charge
(%)
Voltage Effects – Under Voltage
4.2V
Cell Voltage (V)

2V

0V
0 10 20 30 40 50 60 70 80 90 100

State of Charge
(%)
Secondary Cells
Charged
Secondary Cells
Discharging
e- e-
Secondary Cells
Discharged
e- e-
Secondary Cells
Over Discharge
e- e-
Secondary Cells
Charging
e- → e- →
Secondary Cells
Charged
Voltage Effects – Under Voltage
- Anode
- Copper Current Collector Breaks Down

- Self Discharge Rate Increase

- Copper deposits randomly on charging → Potential Short Circuits

- Cathode
- Extended periods below 2V → Gradual Breakdown of Cathode

- Oxygen Released from LCO,LMO → Capacity Loss

- LFP can happen in a few cycles

Temperature Effects – Low Temperature

Activation Energy
Reaction Rate

−𝐸𝑎
𝑘= 𝐴𝑒 𝑅𝑇
Temperature
Chemical Based Constant
Universal Gas Constant
Temperature Effects – Low Temperature

Activation Energy
Reaction Rate

−𝐸𝑎 𝐴
𝑘= 𝐴𝑒 𝑅𝑇 𝑘= 𝐸𝑎
𝑒 𝑅𝑇
Temperature
Chemical Based Constant
Universal Gas Constant
Temperature Effects – Low Temperature

Activation Energy
Reaction Rate

−𝐸𝑎 𝐴
𝑘= 𝐴𝑒 𝑅𝑇 𝑘= 𝐸𝑎
𝑒 𝑅𝑇
Temperature
Chemical Based Constant
Universal Gas Constant

Temperature Reaction Rate, k ?

Temperature Reaction Rate, k ?
Temperature Effects – Low Temperature

Activation Energy
Reaction Rate

−𝐸𝑎 𝐴
𝑘= 𝐴𝑒 𝑅𝑇 𝑘= 𝐸𝑎
𝑒 𝑅𝑇
Temperature
Chemical Based Constant
Universal Gas Constant

Temperature Reaction Rate, k

Temperature Reaction Rate, k
Temperature Effects – Low Temperature

- Reduced Reaction Rate

- Reduced Current Carrying Ability → Slow

Charge/Discharge

- Uptake of Ions slowed → Plating on Anode

** Anytime electrode can’t balance current

flow, plating occurs
Temperature Effects – High Temperature

- Increased Reaction Rate

- Higher Current Output → Higher

Power Output

- Higher Heat Generation, 𝑃𝐻𝑒𝑎𝑡 ∝ 𝐼 2 𝑅

- Positive Heat Feedback

Non-Uniformities

- Manufacturing Defects
- Non-homogenous Coating

- Uneven pressure across electrode

- Delamination of Active material

HOT SPOTS – Uneven Current density

Can lead to Lithium Plating, localised failure leading to thermal run away
Thermal Runaway

youtube.com/watch?v=uN8HcqAtDSY
Thermal Runaway
● Solid Electrolyte Interface (SEI Layer)
Thermal Runaway
● Solid Electrolyte Interface (SEI Layer)
Thermal Runaway
200

135
Temperature (C)

110

80

25

Progression of Thermal Runaway

Thermal Runaway
200

135
Temperature (C)

110

80

25 Overcharge/High T

Progression of Thermal Runaway

Thermal Runaway
200

135
Temperature (C)

110

SEI Layer Breach/Breakdown

80

25 Overcharge/High T

Progression of Thermal Runaway

Thermal Runaway
200

135
Temperature (C)

Electrolyte Breaks down – Flammable Gases Produced

110 No Oxygen

SEI Layer Breach/Breakdown

80

25 Overcharge/High T

Progression of Thermal Runaway

Thermal Runaway
200

Separator Melts
135
Temperature (C)

Electrolyte Breaks down – Flammable Gases Produced

110 No Oxygen

SEI Layer Breach/Breakdown

80

25 Overcharge/High T

Progression of Thermal Runaway

Thermal Runaway
200
Lithium Metal Oxides Breakdown
Oxygen Produced

Separator Melts
135
Temperature (C)

Electrolyte Breaks down – Flammable Gases Produced

110 No Oxygen

SEI Layer Breach/Breakdown

80

25 Overcharge/High T

Progression of Thermal Runaway

Thermal Runaway
GAME OVER
200
Lithium Metal Oxides Breakdown
Oxygen Produced

Separator Melts
135
Temperature (C)

Electrolyte Breaks down – Flammable Gases Produced

110 No Oxygen

SEI Layer Breach/Breakdown

80

25 Overcharge/High T

Progression of Thermal Runaway

Are Lithium Ion Batteries Dangerous?
Are Lithium Ion Batteries Dangerous?
- Lithium Metal

- Usually no free lithium metal present

- During plating minimal quantity

- Thermal runaway not caused by lithium metal

- Biggest Cause of Fires

- Cell Abuse by User

- Cell operated out with operational range

- Handling Damage

- Accidental terminal shorts

Cell Level Safety Devices
-Chemical Design

- Protection Circuits
- Thermal Fuse

- Circuit Interrupt Device

- Pressure

- Pressure Relief Valves

- Pore Closing Separator

Chemical Safety
• Electrodes
• Anode • Slurry Mix – N-Methyl-2-
• Respirators required for pyrrolidone
powder
• Cathode ● R36/38 : Irritating to eyes and
• Respirators required for
skin
powder
● S41 : In case of fire and/or
explosion do not breathe
fumes
● S64 :If swallowed, rinse mouth
with water (only if the person is
conscious)
Chemical Safety
• Electrolyte - Lithium Hexofluorophophate in
Ethylene Carbonate and Diethylene
Carbonate
● R 14 Reacts with water
R 21 Harmful in contact with skin
R 22 Harmful is swallowed
R 41 Risk of serious damage to the eye
R 42/43 May cause sensitization by inhalation and skin contact
● R 43 May cause sensitization by skin contact

● S 2 Keep out of reach from children

● S 8 Keep away from moisture
● S 24 Avoid contact with skin
● S 26 In case of contact with eyes, rinse immediately with plenty
of water and seek medical attention
● S 36 Wear suitable protective clothing
● S 37 Wear suitable Gloves
● S45 Incase of incident seek medical attention
 Lithium Ion
E-Chem Are All
How Cells –
and Cells Cells Made
Are Made Dangerous,
101 Equal?
right?