Smart mobility - creating a circular economy for automotive

lithium-ion batteries

Michal Sura michsoora@gmail.com

One of the main objectives of smart mobility is reducing greenhouse gas

emissions from the transport sector to slow global warming. In 2017, road transport
contributed 21% of the EU's total emissions of carbon dioxide (CO2), the main
greenhouse gas (1). In order to reduce greenhouse gas emissions, it is necessary to
gradually replace fossil-fuel-powered vehicles by zero-emission vehicles. Battery
electric vehicles produce zero direct emissions, and they are very suitable candidates in
the effort to achieve carbon neutrality by 2050. Battery electric vehicles use electricity
stored in a lithium-ion battery pack to power an electric motor and turn the wheels.
Lithium-ion batteries are the most common type of battery used in such vehicles. But in
the next few years the large number of lithium-ion batteries will reach the end of their
life, and it is obvious that their recycling will become very important for environmental
sustainability. The valuable materials within can be recovered, recycled and reused for
producing new batteries. The hazardous chemicals and substances from these batteries
should be disposed of in a safe and legal manner.

Lithium-ion batteries are currently one of the most suitable energy storage for
powering electric vehicles (EVs) with their attractive properties like high energy
efficiency, long cycle life, high power density and high energy density. The number of
EVs worldwide reached 10.9 million in 2020 (2). It is expected that there will be 115
million EVs globally by 2030 (3). Global demand for lithium-ion batteries is predicted to
increase from around 230 GWh in 2020 to 1700 GWh in 2030 (4). In contrast, as of the
end of 2019, the number of fuel cell electric vehicles (FCEV) reached 25210. As can be
seen, electro-mobility based on lithium-ion batteries is currently the best way to reduce
transport's carbon-related emissions. However, modern lithium-ion batteries still have
some performance limits (limited lifespan measured in charge/discharge cycles, service
life, etc.) and technical barriers (high cost, safety, reliability, etc.). Researchers around
the world are working on improving lithium-ion batteries. It is necessary to look for
alternatives to electrode scarce materials (cobalt, nickel, etc.) to increase energy
density and find materials that reduce environmental impact too. Although lithium-ion
battery costs are decreasing rapidly, it is necessary to develop more efficient
manufacturing to decrease their cost. It is clear that only enhanced technological
innovations will ensure the sustainability and commercial viability of lithium-ion battery
systems.
Lithium-ion battery description and working principle

A lithium-ion battery consists of two electrodes (anode and cathode), separated

by a porous non-conductive membrane called a separator which is submerged in a
non-aqueous liquid electrolyte. The electrolyte is an ionically conductive medium which
allows lithium ions to move between the anode and the cathode. The anode and
cathode are separated by the separator which allows lithium ions to move through it, but
not any electrons, in order to prevent a short circuit. The positive electrode of a Li-ion
battery – the cathode is usually made of metal oxides, metal chalcogenides or polyanion
compounds, which can store guest lithium ions.
The negative electrode of a Li-ion battery – anode is usually made of graphite or
silicon-carbon composites. The typical liquid electrolyte for Li-ion batteries consists of
LiPF6 in a mixture of ethylene carbonate (EC) and at least one linear carbonate
selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl
carbonate (EMC) and many additives. The separator for Li-ion batteries is usually a
polyolefin membrane. The anodic current collector is usually made of copper and the
cathodic current collector is made of aluminum.
Discharging:
During the first stage of discharge, lithium atoms oxidize by forming Li+ ions and
electrons, whereas de-intercalated Li+ ions move from the anode to the positive
cathode through the electrolyte and the separator. The electrons flow through an
external wire from the negative anode to the positive cathode, providing electricity in
rechargeable batteries that power an electric motor. At the cathode the electrons
recombine with the Li+ ions and are stored in the molecular structure of the active
material.
Charging:
As the battery is charged, an oxidation reaction occurs at the cathode. The lithium
atoms leave the metal structure and ionize into Li+ ions, and there are lost some
negative-charged electrons. Li+ ions move from the positive cathode to the negative
anode through the electrolyte and the separator. At the surface of the graphite particles,
the Li+ ions and electrons recombine with each other forming neutral lithium atoms and
are reintercalated into the molecular structure of the graphite particles.

The most commonly used lithium-ion battery cathode materials

Lithium Cobalt Oxide(LiCoO2) - LCO

LCO batteries have very high energy density and a

relatively easy manufacturing process. The main
disadvantage of LCO are relatively short life span,
low thermal stability, low specific power and high cost
(because the high cost of cobalt). LCO batteries are
widely used in consumer electronics like mobile
phones, laptops.

Cycle life: 500 - 1000

Specific energy: 150 - 240 Wh/kg

Lithium Manganese Oxide (LiMn2O4) - LMO

LMO batteries have high temperature stability and

safety relative to other Li-ion types. The main
advantages are high rate capability due to low
internal cell resistance which benefits fast charging
and high current discharging. The main
disadvantages are lower capacity relative to
cobalt-based cathodes and relatively short life span.
LMO batteries are usually used in medical devices,
power tools, electric bikes.
Cycle life: 300 - 700
Specific energy: 100 - 150 Wh/kg
Lithium Nickel Manganese Cobalt Oxide
(LiNiMnCoO2) - NMC
NMC batteries have long life cycle and very high
energy density. There is possible to reduce the
expensive cobalt content with some compromise in
performance. A successful combination is NCM532
with 5 parts nickel, 3 parts cobalt and 2 parts
manganese. Other combinations are NMC622 and
NMC811. The main disadvantages are slightly lower
voltage than cobalt systems and higher cost. Adding
a silicon to graphite anode makes it to grow and
shrink through charging and discharging, leading to
mechanical instability of the cell. LMC batteries are
widely used in electric vehicles and energy storage
systems (ESS) that need frequent cycling

Cycle life: 1000 - 2000

Specific energy: 150 - 220 Wh/kg

Lithium Iron Phosphate (LiFePO4) - LFP

LFP batteries have very long life cycle, durability,
excellent safety and low cost. The main
disadvantage are lower nominal voltage which
reduces the specific energy and higher self discharge
than other types lithium-ion batteries which can
cause balancing issues with aging. The cleanliness
in manufacturing process is very important for
longevity.
LFP batteries are used in electric buses or trucks,
where volume or weight is not a problem.

Cycle life: 2500 - 5000

Specific energy: 80 -120 Wh/kg

Lithium Nickel Cobalt Aluminum Oxide

(LiNiCoAlO2) - NCA
NCA batteries have very high specific energy, good
specific power and an average life span. The main
disadvantages are less safety than other Li-ion
battery types (they require extra safety features and
circuits for use in electric cars) and relatively short
life span. NCA batteries cost more in comparison to
other Li-ion battery types. They are used in different
applications like electric cars, power grid
applications, etc.. Tesla deploys NCA batteries in
their electric vehicles.

Cycle life: 500 - 700

Specific energy: 200 - 260 Wh/kg
Lithium Titanate (Li2TiO3) - LTO
LTO batteries have excellent low temperature
discharge characteristics, very long life cycle,
excellent safety, fast charge capability. The main
disadvantages are low density and high cost.
They are used in UPS, military a aerospace
applications.

Cycle life: 3,000–7,000

Specific energy: 50 - 80 Wh/kg

Lithium-ion battery value chain

The lithium-ion battery value chain can be divided into six key segments, starting with
the mining and processing of the raw materials, continues with cell component
manufacturing, battery pack manufacturing, electric vehicle manufacturing and ends
with recycling of the lithium-ion battery packs.

China produced 80% of global battery grade raw materials in 2019. China’s
share in cell component manufacturing accounted for 66% of global production in 2019.
China produced 73% of battery cells globally in 2019. It is obvious that China is the
leader in processing of raw materials, in cell component manufacturing and cell
manufacturing, but only 23% of global supply of all battery raw materials came from
China (6). Europe's share of capacity of cell component manufacturing accounted for
only 6% in 2019 (7).

Key raw materials used to make EV batteries

Lithium and cobalt have the biggest supply risks among the metals used in EV
lithium-ion batteries, whereas aluminum has the lowest. Medium supply risks exist for
manganese, iron, nickel and copper.

Lithium
Lithium is the key component in every lithium-ion battery, all cathodes of
lithium-ion batteries contain the lithium. It is expected that demand for the lithium
carbonate (Li2CO3) that is used in lithium-ion batteries, will start to increase again.
Australia, China and Chile accounted for 88% of global lithium production in 2019 (8).
Lithium is a mineral produced from brines (Argentina, Chile Bolivia) or hard rock
sources (Australia). China produces from both brines and hard rock sources. Total world
lithium production was 82000 tonnes in 2020.
The current price of lithium carbonate (99.5% Li2CO3 battery grade) is 14240 USD per
tonne.

Cobalt
The most cathodes of automotive lithium-ion batteries contain cobalt. More than
70% of the world’s cobalt is produced in the Democratic Republic of the Congo (DRC)
and 15 to 30 percent of the cobalt is produced by artisanal and small-scale mining there
in DRC (9). Russia, Cuba, Australia and Canada, the next largest supply countries,
accounting for just 13% of global supply. Total world cobalt production was 140000
tonnes in 2020. There are preferred chemistries with reduced cobalt content with some
compromise in performance. A successful combinations are NCM532, NMC622 and
NMC811. The current price of cobalt is 42535 USD per tonne.
Nickel
Nickel is the key component in lithium-ion battery that have NCA and NMC
cathodes. There is the focus in low cobalt batteries like NMC 811 and even newly
proposed NMC 9.5.5 batteries (with 9 parts of nickel and 0.5 parts of cobalt and
manganese). Nickel rich cathodes will have certainly an impact on nickel consumption
and the nickel market. Demand for the nickel is expected to grow over the coming
years, it is driven by using the nickel in EV’s lithium-ion batteries. Total world nickel
production was approx. 2.5 million tonnes in 2020. The biggest producents of nickel are
Indonesia, Russian and Philippines. The current price of nickel is 17619 USD per
tonne.

Second life of lithium-ion Batteries

When electric vehicle batteries degrade to 70–80% of their original capacity, it is

necessary to replace them because the residual capacity becomes insufficient for
automotive use. These used batteries could be removed and remanufactured.
Poor-quality cells would be recycled, but high and average-quality cells might be
reused. These cells that passed the quality test can be used in the energy storage
application and live their second life. Such energy storages allows renewable energy
sources (solar panels, wind turbines, etc.) to store generated electric energy and
support the electric grid with electricity during peak demand hours.
Recycling

There are several ways to recycle lithium-ion batteries. Generally, two recycling
methods for lithium-ion batteries exist hydrometallurgy and pyrometallurgy.
Hydrometallurgy is based on aqueous chemistry, typically at low temperatures,
typically have a high extraction rate, a high metal selectivity and a low energy
consumption. Hydrometallurgical processes consists of several steps. The metals are
dissolved with the help of an acid or salt. Another step is purification where metals are
separated via selective chemical reactions. In the last step, the metals are recovered
from the solution as a solid product in a form of metals, salts or a compound, by
crystallization, electrochemical or electrolytic reduction, etc. This process needs large
plant sizes, there are utilized concentrated acids, which easily generates large amounts
of waste solutions. Under the optimal conditions, the recovery percentages of Ni, Co,
Mn, and Li can reach 98%, 97%, 98%, and 89%, respectively.
Pyrometallurgy needs high-temperature processes such as roasting or smelting
for recovering cobalt, nickel, copper, aluminium and iron. Pyrometallurgy has
advantages such as high reaction rates, small plant size for a given throughput, and a
high overall efficiency. The high temperatures needed in the processes lead to high
energy consumption and emissions. In addition, the recovery of lithium is very difficult.
These processes often only produce intermediates that require further
hydrometallurgical process.
1, https://ec.europa.eu/clima/policies/transport/vehicles_en
2,https://www.automotiveworld.com/news-releases/zsw-electric-cars-on-the-rise-global-count-climbs-to-10-9-million/
3, https://www.statista.com/statistics/970958/worldwide-number-of-electric-vehicles/
4,https://ihsmarkit.com/research-analysis/threefold-increase-in-recycling-needed-to-help-meet-2030-deman.html
5, https://www.iea.org/reports/hydrogen
6,https://www.benchmarkminerals.com/membership/china-controls-sway-of-electric-vehicle-power-through-battery-ch
emicals-cathode-and-anode-production/
7,https://www.spglobal.com/marketintelligence/en/news-insights/blog/top-electric-vehicle-markets-dominate-lithium-io
n-battery-capacity-growth
8, https://www.nsenergybusiness.com/features/top-lithium-producing-countries/
9, https://www.cfr.org/blog/why-cobalt-mining-drc-needs-urgent-attention
10, https://pubs.usgs.gov/periodicals/mcs2021/mcs2021.pdf
11,https://www.researchgate.net/publication/267931433_Hydrometallurgical_process_for_the_recovery_of_metal_val
ues_from_spent_lithium-ion_batteries_in_citric_acid_media