Industrial batteries. Features Summary.
Chapter 3 – Lithium Ion battery types
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To read Chapter 1, please visit: https://www.norwatt.es/noticia‐industrial‐
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To read Chapter 2, please visit: https://www.norwatt.es/noticia-industrial-
batteries--features-summary--chapter-2---industrial-battery-types-es.html
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Commercially, there are five types of lithium-ion batteries depending on the
cathode material and another two depending on the material of the anode
material.
Working Principles
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Cells convert chemical energy into electrical energy (and vice-versa). In
Lithium ion batteries, during cell charge, the lithium ions flow from the
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cathode to the anode and they are stored there. During cell discharge, lithium
ions disassociate from the anode and flow to the cathode through the
electrolyte and electrons are transported by the external circuit to do an
effective work.
A lithium ion battery has three functional layers: the positive electrode
(cathode), the negative electrode (anode), and the separator.
The anode corresponds to the negative electrode. The electrons leave the
battery through the anode; therefore, it must be made of a material with high
electronic conductivity and great cycling capacity. Graphite is generally used.
(70 to 250 micron)
The cathode corresponds to the positive electrode and must be capable of
accepting and releasing lithium ions and electrons. Cathodes are generally
made of metallic lithium oxide which can oxidize when lithium is removed.
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For example: LiMO2, (M = cobalt (Co), nickel (Ni), or manganese (Mn)). (70
to 250 micron)
The mode of transporting lithium ions between electrodes during charging
and discharging is the electrolyte; that’s why it has to be a good ionic
conductor and a good electronic insulator. The electrolytes are usually made
up of a solution of lithium salt in an organic solvent; for example: lithium
hexafluorophosphate (LiPF6) with ethylene carbonate and methyl carbonate
(EC-DMC).
[email protected] The membrane that separates the anode and the cathode is called the
separator and it is the host of the electrolyte. The separator prevents short
circuits between anode and cathode but allows the Li ions to flow during
charging and discharging. (20 to 25 micron)
Batteries can be classified by energy and power. This classification is marked
by the composition and characteristics of the electrodes and their materials:
Energy for long time discharge and power for high current discharge.
High Power cells – can discharge at rates 10 to 100C rate (from 6 min to <1
High Energy cells – can discharge at 2C rate (30 min) or less but energy
content
High Energy cells – can discharge at 2C rate (30 min) or less but energy
content exceeds 170 to 190 Wh/kg
Energy storage capacity of a battery: depends on the number of active
components that the electrodes can store.
Power capacity: is a function of the surface area of the electrodes and the
internal resistance of the battery.
These energy and power ratings depend on and are related to each other.
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The rate-C represents this energy / power ratio (it is the data that allows
knowing how a battery is charged or discharged in relation to its maximum
capacity). It should be added that the energy density depends on the
chemistry of the battery, while the power density depends on the kinetics and
the design of the cell. Thin electrodes can provide high power densities, and
thick electrodes produce high energy densities. This is why batteries can be
designed to supply high power or high energy depending on the needs.
3.1 POSITIVE CONTACT: CATHOTE OPTIONS
The positive electrode is called the cathode and typically defines the chemical
type of the battery. It is built with an aluminium full coated in both sides with
a lithium metal oxide compound and binder
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Generally, research into lithium ion batteries is being carried out to find an
economical material, with better cyclic performance, good thermal stability
and conductive to high energy and power densities. In particular, thermal
stability is a major concern when selecting cathode materials since heat
generation at the cathode is three to four times greater than that of the
anode.
3.1.1 Lithium cobalt oxide (LCO) (LiCoO2)
[email protected] LCO has high energy density per unity mass, but is not well suited for use in
off-grid products because of lower cycle life and poorer safety. Nonetheless,
LCO batteries are ubiquitous and still frequently used for these applications.
Characteristic LiCoO2 (LCO)
Nominal voltage per cell 3,7 Vdc (4,2 Vdc 100% SOC)
Specific energy (Wh/kg) 175-200
Energy density (Wh/L) 400-640
Cycle life (to 80% original capacity 500
at 100% DOD)
Calendar life (years) >5
Ambient temperature during 0-45
charge (°C)
Ambient temperature during -20-60
discharge (°C)
Self-discharge capacity loss 2-10%
per month
Memory effect No
Toxic metals No
Battery management Yes
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system required
Main disadvantages:
Relatively short life span
low thermal stability
Limited load capabilities.
The Li-cobalt is losing favour to Li-manganese, but especially NMC and NCA
because of the high cost of cobalt and improved performance by blending
with other active cathode materials.
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Li-cobalt excels on high specific energy but offers only moderate performance
specific power, safety and life span.
LCO technology LiCoO2 available here, please check:
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batteries-saft-rechargeable-lithium-ion-battery-en.html
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3.1.2 Lithium manganese oxide (LMO) (LiMn2O4)
Pure LMO batteries have good thermal stability and safety but lower cycle
life; they have been replaced by blending the manganese oxide with nickel
and cobalt (NMC).
Characteristic LiMn2O4 (LMO)
Nominal voltage per cell 3.70V (3.80V) nominal; typical
operating range 3.0–4.2V/cell
Specific energy (Wh/kg) 100-150
Energy density (Wh/L) 150-300
[email protected] Cycle life (to 80% original capacity 300-700
at 100% DOD)
Calendar life (years) >5
Ambient temperature during 5-45
charge (°C)
Ambient temperature during 5-45
discharge (°C)
Self-discharge capacity loss ---
per month
Memory effect No
Toxic metals No
Battery management Yes
system required
Main advantages:
Improved current handling
Lower internal resistance
High thermal stability
Enhanced safety
Main disadvantages:
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The cycle and calendar life are limited.
Li-manganese has a capacity that is roughly one-third lower than Li-cobalt.
Design flexibility allows engineers to maximize the battery for either optimal
longevity (life span), maximum load current (specific power) or high capacity
(specific energy).
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Although moderate in overall performance, newer designs of Li-manganese
offer improvements in specific power, safety and life span.
3.1.3 Nickel cobalt aluminium (NCA) LiNiCoAlO2
NCA has the highest energy density per unity mass. Like LCO and NCA
batteries, it has lower thermal stability than competing technologies. It
shares similarities with NMC by offering high specific energy, reasonably good
specific power and a long-life span.
Characteristic LiNiCoAlO2 (NCA)
Nominal voltage per cell 3.60V nominal; typical operating
range 3.0–4.2V/cell
Specific energy (Wh/kg) 200-260
Energy density (Wh/L) 200-250
Cycle life (to 80% original capacity 500
at 100% DOD)
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Calendar life (years) >5
Ambient temperature during 0-40
charge (°C)
Ambient temperature during 0-40
discharge (°C)
Self-discharge capacity loss --
per month
Memory effect No
Toxic metals Yes
Battery management Yes
system required
Main advantages
High specific energy
Reasonably good specific power
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Long life span
NCA cathodes contain the most energy amount by weight and volume
(as NMC).
Main disadvantages:
Less safety than other Li-ion battery types (they require extra safety
features and circuits for use in electric cars for example)
Higher cost in comparison to other Li-ion battery types
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High energy and power densities, as well as good life span, make NCA a
candidate for EV powertrains. High cost and marginal safety are negatives.
NCA technology LiNiCoAlO2 available here, please check:
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https://www.norwatt.es/products/batteries-and-accessories-lithium-ion-
batteries-saft-evolion-en.html
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3.1.4 Lithium nickel manganese cobalt oxide LiNiMnCoO2 (NMC)
One of the most successful Li-ion systems is a cathode combination of nickel-
manganese-cobalt (NMC). The secret of NMC lies in combining nickel and
manganese.
NMC blends offer combinations of good cycle life, safety, and high energy
density. The ratios of elements can be tailored to emphasize qualities that
target specific applications including off-grid products.
Battery manufacturers move away from cobalt systems toward nickel
[email protected] cathodes because of the high cost of cobalt. Nickel-based systems have
higher energy density, lower cost, and longer cycle life than the cobalt-based
cells but they have a slightly lower voltage.
NMC batteries are widely used for power tools, energy storage
systems (EES) which need frequent cycling and electrical power-trains like
automotives. The cathode combination typically used is 1-1-1 which
means one third nickel, one third manganese and one third cobalt. This
reduces the raw material cost due to lowered content of cobalt. Other
combinations are also possible.
Characteristic LiNiMnCoO2 (NMC)
Nominal voltage per cell 3.60V, 3.70V nominal; typical
operating range 3.0–4.2V/cell, or
higher
Specific energy (Wh/kg) 150-220
Energy density (Wh/L) 205-300
Cycle life (to 80% original capacity 1000-2000
at 100% DOD)
Calendar life (years) >10
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Ambient temperature during -10 + 45
charge (°C)
Ambient temperature during -10 +45
discharge (°C)
Self-discharge capacity loss 0,35 – 2,5
per month
Memory effect No
Toxic metals Yes
Battery management Yes
system required
Main advantages:
NMC cells provide longer life cycle
Lower cost
Higher energy density
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NMC cathodes contain the most energy amount by weight and volume.
Main disadvantages:
Adding silicon to graphite has the downside of making the anode grow
and shrink through charging and discharging, leading to mechanical
instability of the cell.
Slightly lower voltage than cobalt systems
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NMC has good overall performance and excels on specific energy. This battery
is the preferred candidate for the electric vehicle and has the lowest self-
heating rate.
NMC technology LiNiMnCoO2 available here, please check:
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3.1.5 Lithium Iron Phosphate (SLFP, LFP) LiFePO4
LiFePO4 batteries exhibit qualities that make them ideally suited for off-grid
products where cost, safety, stability, and cycle life are primary requirements.
It does not release oxygen, which makes it a safe material to use with better
thermal stability.
LFP is more tolerant to full charge conditions and is less stressed than other
lithium-ion systems if kept at high voltage for a prolonged time. As a trade-
off, its lower nominal voltage of 3.2V/cell reduces the specific energy below
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that of cobalt-blended lithium-ion. With most batteries, cold temperature
reduces performance and elevated storage temperature shortens the service
life, and Li-phosphate is no exception. Li-phosphate has a higher self-
discharge than other Li-ion batteries, which can cause balancing issues with
aging.
The LiFePO4 batteries can improve electrochemical performance is to nano-
structure LiFePO4 particles or coating the cathode with Sn.
Characteristic LiFePO4 (LFP)
Nominal voltage per cell 3.20, 3.30V nominal; typical
operating range 2.5–3.65V/cell
Specific energy (Wh/kg) 90-120
Energy density (Wh/L) 125-250
Cycle life (to 80% original capacity 1000 – 2000 (can retain 95%
at 100% DOD) capacity after 1000 cycles)
Calendar life (years) >5
Ambient temperature during 0-45
charge (°C)
Ambient temperature during -30-60
discharge (°C)
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Self-discharge capacity loss 2-10
per month
Memory effect No
Toxic metals No
Battery management Yes
system required
Main advantages:
Improves power and energy
Allows for floating at less than 100% SOC
Enables accepting REGEN
Improves electronics performance
Improves overcharge tolerance
Excellent safety
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Main disadvantages:
More tolerant to conditions of full charge and is less stressed at higher
voltage for a long time.
lower nominal voltage which reduces the specific energy
Higher self-discharge than other types Li-ion batteries, which causes
balancing issues with aging.
[email protected] Li-phosphate has excellent safety and long life span but moderate specific
energy and elevated self-discharge.
SLFP technology LiFePO4 available here, please check:
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https://www.norwatt.es/products/batteries-and-accessories-lithium-ion-
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3.2 NEGATIVE CONTACT: ANODE OPTIONS
Anode composition and electrochemical properties are very important to the
performance of a battery. For the anode material to be effective, high
electronic conductivity, low working potential, high cycle stability and low
volume change are required during lithium insertion and extraction.
In order to be suitable for lithium-ion battery manufacturing, anode
materials should meet the following requirements:
[email protected] Excellent porosity and conductivity.
Good durability and light weight.
Low Cost.
Voltage match with preferred cathode.
During initial Lithium ion battery operation, the SEI (solid
electrolyte interphase) layer forms on the graphite surfaces, the most
common anode material. The SEI is essential to the long-term performance
of LIBs, and it also has an impact on its initial capacity loss, self-discharge
characteristics, rate capability, and safety. While the presence of the anode
SEI is vital, it is difficult to control its formation and growth, as they depend
on several factors. These factors include the type of graphite, electrolyte
composition, electrochemical conditions, and temperature.
3.2.1 Carbon based anodes
Graphite formulations (A cooper foil coated with natural graphite, synthetic
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graphite or amorphous carbon) are used for the negative electrode in the
majority of Li-ion commercial cells.
Graphite and carbon-based anode materials have been used in commercial
Li-ion cells since 1991 because of the good electrochemical properties, low
cost, and nontoxicity of graphite.
During the first charge cycle a solid electrolyte interphase layer (SEI) forms
in the graphite surface that helps to stabilize the molecular structure and
prevent it from reaching with the liquid electrolyte.
The SEI layer stabilizes the anode by preventing reactions between the
graphite and the electrolyte. SEI layer integrity plays an important role in cell
performance. The SEI can therefore be described as a protective layer.
The secondary SEI mainly consists of Li2CO3 and LiF. It has been suggested
that besides the formation of the secondary SEI, a new organic SEI is formed
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by solvent reduction. These complex processes of SEI formation and change
occur up to a temperature of approx. 200°C.
3.2.2 LTO cells
The LTO (Li4Ti5O12) is bringing a new dimension of possibilities for the
energy storage with a number of economical as well as ecological aspects.
With applications in many sectors, with a primary focus on high speed
charging and energy storage, LTO technology is the future of battery-
powered technology.
[email protected] LTO cells offers very high cycle life, excellent thermal stability, excellent
safety, and good low temperature operation. LTO can be used with NMC or
LMO cathodes.
LTO does not react with organic electrolytes, therefore SEI is not formed
which makes it highly thermal stable and an excellent choice for large scale
battery anode material.
Main advantages:
More than 7000 charge discharge cycles
Excellent hight and low temperature performance
Extremely long lifetime
Rapid battery charging and discharging
Enhanced safety
Low-temperature performance
Integration with energy storage
Main disadvantages:
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Lower inherent voltage (2.4 V) than other Li-ion technologies
Lower specific energy than other Li-ion technologies
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3.3 ELECTROLYTE AND SEPARATOR
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The battery separator is an essential component of batteries that strongly
affects their performance. The control of their properties being particularly
important for obtaining lithium-ion batteries with high cycling performance.
Separators are placed between both electrodes, should show high ionic
conductivity, excellent mechanical and thermal stability.
Electrochemical performance of the batteries is highly dependent on the
material, structure, and separators used. Most common separators are
polypropylene (PP) monolayer and
polypropylene/polyethylene/polypropylene (PP/PE/PP) trilayer.
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The electrolyte is a lithium salt dissolved in an organic solvent. A liquid
electrolyte acts as a conductive pathway for the movement of cations
passing from the negative to the positive electrodes during discharge.
Recent advances in battery technology involve using a solid as the
electrolyte material. The most promising of these are ceramics. The main
benefit of solid electrolytes is that there is no risk of leaks, which is a
serious safety issue for batteries with liquid electrolytes.
Coming soon… Chapter 4 - Lithium ion cells construction
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