Lecture #4

Tailpiece: lithium-ion tidbits

T Prem Kumar
[email protected]
Quo vadis, lithium?
 What is the foreseeable battery fleet?

Vehicles (109 vehicles in 2015)

Massive electrification: 109 x 30 kWh = 30 TWh of storage

Renewable energy storage (for solar, wind, … )

9–30 TWh (Barnhardt & Benson, 2013)

Global battery fleet: 50 TWh

(It will take 140 years at today’s lead-acid production rate!)

Do we have the resources?

Growing demand for battery metals
 Quo vadis, lithium?
>60% of world reserves atop the Andes:
The Lithium ABC (Argentina-Bolivia-Chile)
(Salt pans: salars)

Hard rock sources: spodumene, hectorite,

lepidolite, pegmatite, petalite.

Oceans: 230 billion tonnes of lithium

Li in the oceans: 0.17 ppm
Salar de Atacama (Chile): 1000−3000 ppm.

Mg:Li in seawater: 7000:1

Salar de Atacama: 6.4:1
Mg and Li: similar chemistries
Global lithium deposits (metric tonnes)
(as of January 2011 – US Geological Survey)
Identified resources Reserves
Bolivia 9,000,000
Chile 7,500,000 7,500,000
China 5,400,000 3,500,00
United States 4,000,000 38,000 Reserves: mineral
Argentina 2,600,000 850,000 sources that can be
Brazil 1,000,000 64,000 legally and economically
Congo 1,000,000 extracted.
Serbia 1,000,000
Australia 630,000 580,000 Resources: known
Canada 360,000 mineral deposits.
Zimbabwe 23,000
Afghanistan: mineral
Portugal 10,000 deposits of ~1 trillion USD
TOTAL 32,490,000 12,565,000 (Li, Co, Ni, Cu, Ag).
Hand-scrapped lithium-rich salt piles on Bolivia’s Salar de Uyuni.
Lithium: the darling of the Western green lobby (Salar de Uyuni).
Salar de Uyuni: world’s key to the electric vehicle!
Can lithium go the distance?
End of the road for lithium?

Lithium-ion batteries have only 0.5–1.0 wt.% of Li.

Recycling Li from spent batteries is not an option

especially when ‘virgin’ lithium sources are plentiful.

Metals such as Co (36±9 wt.% in C/LiCoO2 batteries)

can be recycled with simple chemistries.

Lectro® Max 100: stabilized lithium metal powder (SLMP): 98%

 PetroLithium: a game changer
Petroleum brine: long known to contain minerals; but the by-product is
sent back downhole after oil is separated at the wellhead.

Every barrel of oil comes with 25–250 times that volume of water.

The N. American O&G industry produces 80–100 million barrels of

brine every day.
This water is rich in metals such as lithium, manganese, ... .
It contains 75–140 mg/litre of lithium.

Lithium can be extracted from this brine

by coagulation–nanofloatation–filtration

Lithium is the new gasoline.

 The grass always looks greener on the other side, but
alternative technologies should be carefully examined for their
long-term sustainability. The oil-to-lithium switch reminds us of
Woody Allen’s words: “More than any other time in history,
mankind faces a crossroad. One path leads to despair and utter
hopelessness. The other, to total extinction. Let us pray we
have the wisdom to choose correctly.”
Charging lithium-ion batteries
The charger, battery and load are connected in parallel

Let the charging current be Ic,

the current into or out of the battery be Ib, and
the current through the load be IL.
Load resistance and current IL are constant.
The current through the charger Ic = Ib + IL
(by Kirchoff’s current law; assume negligible internal resistance for the charger).

Thus, the battery is charging, and the load gets its current from the
charger, and not from the battery.

Note the charging current is proportional to the amount the battery has discharged.
The internal resistance of the battery is lowest when fully discharged
and highest when fully charged.
[A] When battery is fully charged
There is no charging current into the battery.
At this point, the battery will also discharge through the load: IL = Ic + Ib.
The ratio of Ib to Ic depends on the internal resistances of the charger and the battery.

[B] When a battery is being charged

The charger (a) powers the load and (b) charges the battery.
As the battery gets fully charged, the charging current drops to zero.
After that the current through the battery reverses and discharges through the
load. This discharges the battery so it gets charged from the charger.
Actually the systems stops at a point of equilibrium where there is no battery current
involved.
The charger powers the load as long as the battery does not drain or charge.
• Constant voltage charging (switches off when current drops)
• Constant current charging (switches off at cut-off voltage)
• Taper current charging (CV; current drops as the cell voltage builds up)
• Trickle charging (CC; to compensate for the self-discharge)
• Float charging (battery and load permanently connected in parallel with
DC source; voltage kept below an upper voltage limit. Used in UPS.)

• Pulse charging (with 20–30 ms rest; allows chemical actions to stabilize)

• Burp/reflex/negative pulse charging (pulse charging with 5 ms discharge
to depolarise; to dislodge gas bubbles)
• IUI charging (used for fast charging standard flooded lead acid batteries)
• Random charging (to charge only when possible)
Trickle stage
LiB discharge limit: 2.8–3.0 V. Below 3V: battery is said to be in a dead
state. To overcome dead state, battery is charged at 0.1–0.3C.
If a dead battery does not charge in ~10 min, it is permanently damaged.
CC stage
Charged at a constant current, with the voltage not exceeding the peak
terminal voltage. The value of the current for charging the battery is
decided by its C. Generally, the charging rate is 0.5–0.8C. In this stage, the
battery gets charged fast, to up to 80% (aka fast charging stage).
CV stage
When the terminal voltage reaches 4.2V, the battery is charged at a
constant voltage (= voltage of a fully charged battery). The charging
current starts decreasing. So it takes more time to charge the remaining
20% of the battery.
There are three states in lithium-ion battery charging:
1. Trickle charge stage
2. Constant current stage (CC state)
3. Constant voltage stage (CV state)
Transfer of energy from EV batteries to grid/home during daylight hours (peak demand)
and returning it to EVs during night hours (low demand)

Problems
Inconvenience
Bi-directional charging stations (inverters with precise V & freq. regulators)
Massive support system to manage distributed power and buy-back billing
Luring of attractive buy-back tariffs for cycle-life loss of expensive batteries
Disruption of work schedule if energy is not returned in time to the EV
Reluctance to embrace EVs

Despite the hype, market penetration of EVs remains stubbornly low.

Fuel costs of EVs: much lower than gasoline.

But high price of batteries: a big deterrent.

Another major impediment to sales is charging anxiety.
EV outlook and battery price
 Car price vs. battery price

LiB packs for cars: $1,160/kWh (2010) — $176 (2018)*

How does it translate for a car?

Tesla Model 3**: $90,000 (2010) — $13,000 (2019)*

*inflation-adjusted prices
**battery capacity: 75 kWh
Charging anxiety can be explained by the concerns on obsession with range.

• Where can I charge my battery?

• Will my connector fit the one at the charging station?
• How long will charging take?
• Will my car register on the network?
• Will quick charging be available?
• Will there be a queue?
• Will there be good batteries for swapping?
 Fast charging

EV market: ∼1% of annual light-duty vehicle sales

Reluctance to embrace EVs: range anxiety

(fear that EVs may run out of juice on a trip → passenger left stranded)

An enabler for mainstream adoption of EVs: fast charging.

A BMW–Daimler–Ford–Volkswagen JV (2017)
to deploy 400 “ultrafast” charging stations across Europe by 2020
(with power up to 350 kW, able to charge a 200-mile-range:
e.g., Chevy Bolt with 60-kWh, 435 lb battery) in ∼10 min.
 Fast charging and temperature
No EV today allows fast charging in cold/cool temperatures:
lithium plating* → reduced battery life & even safety hazards.
EVs should allow quick recharge anywhere in any weather .

Gr/LiFePO4 cell (for 8% capacity loss) Nissan Leaf (owner’s manual)

Temperature Cycles Temperature Rate Duration
25ºC 2,800 25ºC 2C 30 min
15ºC 1,800 10ºC 0.6C 90 min
10ºC 350 For 80% charge

47 out of 50 US states: winter temperature below 10°C.

*Large anode polarization pushes anode potential below threshold for lithium plating.
[J. Wandt, P. Jakes, J. Granwehr, R.A. Eichel and H.A. Gasteiger, Mater. Today 21 (2018) 231;
Z. Li, J. Huang, B.Y. Liaw, V. Metzler and J. Zhang, J. Power Sources 254 (2014) 168.]
Fast charging in cold climes – a new invention

Enables 15-min fast charging at any temperature (even −50°C).

LFP (lithium plating free) cell

15 min – 80% capacity – 0°C – 3.5C – 4,500 cycles (90X boost).
Equivalent to >12 y and >280,000 miles of EV lifetime.

X.G. Yang, G. Zhang, S. Ge and C.Y. Wang, Proc. Natl. Acad. Sci. 115 (2018) 7266.
Lithium plating-free batteries

Self-heating lithium-ion battery

Two PET-coated Ni foils sandwiched between 2 single- Linear dependence of the resistance
sided anodes. One foil is connected to the negative of Ni foil on temperature
terminal; the other foil forms an activation terminal,
and is connected via a switch to the positive terminal.

X.G. Yang, G. Zhang, S. Ge and C.Y. Wang, Proc. Natl. Acad. Sci. 115 (2018) 7266.
Infernal batteries
 Lithium batteries in the crosshairs
Lithium-ion batteries are statistically very reliable.
With just one in 10–40 million failures, reliability is not a problem.
Failures are an exception.
Yet exceptions can still be dangerous.

The MH370 Crash

A deadly cargo of mobile phone

batteries caught fire and caused a
catastrophic explosion that brought
down the Malaysian Airways jet.

About 500 lbs of Motorola batteries

in the Boeing 777 led to the crash
and killed all the 239 passengers on
board (March 8, 2014).
 Collection & recycling lithium-ion cells

No mechanism yet for proper collection

and segregation of spent LiBs.

Massive fire caused by improper disposal of

LiBs at a railway dumpyard (Queens, Hollis, NY)
Battery disposal
◼ High risk of fire with surrounding paper/organics.

◼ Do not discard as trash.

◼ Drop-off highly recommended.
◼ Make sure the batteries are taped/insulated when collecting.
 Stranded energy in LiBs

Stranded energy is the energy remaining in a ‘discharged’ battery.

It presents a hazard to emergency responders.

Mitigating the hazard of stranded energy remains an unresolved issue.

Stranded energy in ICEVs can be drained by emptying the fuel tank and
relieving the pressure in the fuel system.

There is no standardized procedure to drain LiBs down to a 0% SOC.

 Safety issues with
damaged/‘spent’ batteries
Batteries discarded after use are not fully discharged.

Risks
Electric shock/flash
Toxic leaks
Fire/deflagration

Electric shock: a risk to workers/responders as LiBs cannot be ‘turned off’.

Arc flash / burn injury is possible for systems with 100V and above.
Toxic solutions can leak out of damaged batteries.
LiBs kept above 80ºC generates heat at a faster rate than they can dissipate
→ spew of flammable gases → thermal runaway. Deflagration hazards are
higher in confined spaces. One way out: ventilation.
 Stranded energy: possible solutions
Suitcase solution: Create a physical connection to the battery pack.
Equip tow-trucks with a discharge tool with a pluggable port.
Discharge battery to a safe level.

Internal safety: Create an internal safety circuit in the battery pack.

But is it feasible, at what cost?
Will it work in a damaged battery?

Internal safety circuits can help battery shutdown in case of a crash.

(airbag analogy).

https://chargedevs.com/features/ev-standards-gaps-delayed-battery-overheating-and-
stranded-energy/
Are EVs less safe than ICEVs in a crash?
Short answer: Yes.
Not because the batteries are unsafe.

We still don’t know how to handle a crashed EV!

Exposed leads can lead to shock/arcing.

Firefighters are ill-prepared with LiB fires.
They are not equipped with Class D extinguishers.

Safety standards have not kept pace with advancements in EV technology!

Burning paper Flammable liquids: Energized Combustible Kitchen fires
lumber gasoline kerosene electrical metals & organo-
cardboard organic solvents equipment: metallics:
plastics appliances magnesium
switches sodium, lithium
panel boards titanium Grignard
power tools reagents

REACTIVE
METAL FIRE
 Fighting lithium fire
Class D fires are extinguished by simple smothering.

Class D extinguishing agents: NaCl, graphite powder, Cu powder

NaCl: For Mg, Na, U, Al fires. (Not for Li.)

NaCl cakes under heat, forms a crust, and excludes air & dissipates heat.

Graphite (for high-m.p. metal fires: Zr, Ti). Also for Li.

The best choice for lithium fires: Cu powder.

The only known lithium fire fighting agent that can cling to vertical
surfaces, making it suitable for 3-D and flowing fires.

Cu powder D-type extinguishers come with a low-velocity applicator (ensures that

no burning metal gets blown around).
 LiB fires vs. Li fires
Lithium-ion battery fires can generally be suppressed with water and Halon.

Water douses flames and suppresses propagation of thermal runaway.

Halon 1211 knocks down flames.
(Halon 1211 alone cannot prevent re-ignition as thermal runaway can still
propagate.)

In a typical FAA test, Halon 1211 extinguished flames from a phosphate cell,
but could not put out flames from a cobalt oxide cell.

Halon 1301 (bromotrifluoromethane)

Least toxic of the Halon family; most superior fire suppressant.

It knocks down fire not by displacing oxygen, but by terminating chain-

branching reactions of gas-phase hydrocarbon combustion.

Br: confers fire retardant properties; interferes with the chain-branching

reactions
 Fighting the fire-throwers
Foam-based extinguisher

For lithium-ion battery fire

Use a foam extinguisher, CO2,
ABC dry chemical, graphite
powder, Cu powder, or Na2CO3 –
as for other combustible fires.
Allowing a lithium-ion battery
pack to burn in a controlled
manner is also an option.

Class D only for lithium-metal fires

Electrical energy in LiBs
o Example: A prismatic cell with specifications

◼ 3.7 V
◼ 2.96 Wh
◼ 800 mAh

◼ Energy (Wh) = capacity (Ah) x voltage (V)

◼ = 0.8 Ah x 3.7 V
◼ = 2.96 Wh

o 1 Wh = 3.6 kJ
o Stored energy = 2.96 Wh x 3.6 kJ/Wh = 10.65 kJ
Chemical energy in LiBs
(available for combustion)
Example: A prismatic cell (previous slide)
Electrolyte: 1–5 g of DEC
Separator: 0.5–1 g

◼ DEC heat of combustion: 20.92 kJ/g

(21–105 kJ of energy from electrolyte combustion)
o
◼ PP heat of combustion: 42.66 kJ/g
(21–42 kJ energy from separator combustion)

o Total chemical energy in the cell: 42–147 kJ

Stored energy in small prismatic cells
o Estimate of total energy released is 52 to 117 kJ

Energy Lower Higher Amount

limit (kJ) limit (kJ) (g)
Chemical energy of combustible materials 42 147
(total)

Separator 21 42 0.5 to 1

Electrolyte 21 105 1 to 5

Electrical energy 10.65 12.1

(nominal voltage and 100% SOC)

Total 52.65 117

 Stored energy in 18650 cells
Specifications o

◼ 3.7 V ◼ DEC heat of combustion: 20.92 kJ/g

◼ 9.62 Wh ◼ PP heat of combustion: 42.66 kJ/g
◼ 2600 mAh

Energy Lower Higher Amount

limit (kJ) limit (kJ) (g)
Chemical energy pf combustible materials 122 235.61
(Total)
Separator 59.72 68.25 1.4 to 1.6

Electrolyte 62.36 167.36 3 to 8

Electrical (nominal voltage to 100% SOC) 34.62 39.3

Total 157 207

*For comparison, a 190 g stick of dynamite can release 1 MJ of energy.

LiBs – cradle to grave
 Lithium-ion battery lifecycle
o Manufacturing
◼ Formation cycling
◼ Factory exit at a moderate SOC
o Transportation
o Warehouse storage
o Pack/device assembly
◼ Battery pack
 Protection devices
 Pack testing
o Pack shipment
o Installation in device (EV)
◼ Device testing
o Device shipment (distributors – customers)
o Device usage
◼ Second use
o Device/battery end of life
◼ Discarding / recycling
 LiB transportation
o Many failures are related to
(i) improper packaging (mechanical damage, external shorts)
(ii) shipment procedures

o Shipment as per
International Air Transportation Association (IATA) guidelines
for dangerous goods

o UN 38.3 certification is a must for LiB transportation

◼ LiBs (not part of equipment): SOC less than 30%.
◼ Cannot be part of cargo of passenger aircraft.

http://www.iata.org/whatwedo/cargo/dgr/Documents/lithium-battery-shipping-guidelines.pdf
 Storage & handling
o Follow procedures for safe handling of lithium-ion batteries
o Protect from short-circuit, high temperature
o Pouch cells must be recessed in packaging trays
 LiB: disposal and recycling

o At present, recycling lithium from spent batteries is not

an option (Li: 1–1.5% of cell mass)
o Cobalt (and nickel) are costly; worth recycling
(Co: 38–40% of cell mass)

o Dispose used cells properly.

o Battery recycling resources: https://www.call2recycle.org

A.K. Shukla and T. Prem Kumar, J. Phys. Chem. Lett. 4 (2013) 551.
LiB characteristics
Chemistry LCO NMC LFP LMO

Nominal voltage (V) 3.6–3.7 3.6–3.7 3.2–3.2 3.6–3.7

Charging 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 2C >30C >30C

(Best result) (<1C) (<10 C) (<10 C)

Specific energy (Wh/kg) 150–250 90–120 100–150

Thermal runaway onset (ºC) 150 210 >270

In use since 1991 2003 1999 1996

Designation ICR INR IFR IMR

 Thank you
for your attention!

Workshop on Electric and Hybrid Vehicle Engineering (Oct. 18&19, 2019)

Workshop on Battery Technology for E-vehicle (Dec. 26–28, 2019)
Indian Institute of Information Technology Design and Manufacturing, Kancheepuram.