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MAUE602L – Battery and Fuel Cell
Module IV
Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
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Batteries and Fuel Cells - Module IV 22-03-2024
Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Unlike sealed lead acid (SLA) and NiCd, Li-ion batteries do not
contain toxic heavy metals.
Although lower in specific energy than lithium-metal, Li ion is safe,
provided the voltage and currents limits are being respected
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Batteries and Fuel Cells - Module IV 22-03-2024
Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
The membranes have extremely small pores that allow the ions to
move within the cell.
Have a high voltage output of 3.6 Volts
Compounds used in the cell determines the energy density of the cell.
Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
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Batteries and Fuel Cells - Module IV 22-03-2024
Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Cylindrical Cells
Li-ion cylindrical cells are made by rolling long
strips of cathode foil, separator, and anode foil
together and inserting into a rigid stainless steel or
aluminum cell housing or “Can”.
Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Prismatic Cells
Prismatic cells are similar in construction to cylindrical
cells but use a flat rectangular housing to lower the
overall thickness of the cell.
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Batteries and Fuel Cells - Module IV 22-03-2024
Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Pouch Cells
They are composed of rectangular stacks of individual
electrode/separator layers, but instead of a rigid metal
case they use a laminated flexible polymer/aluminum
“bag”.
The electrodes have tabs along one side; these are
welded together with battery terminal tabs that stick out
of the top of the bag.
The assembly is saturated with a liquid electrolyte and
the bag is heat-sealed.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
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Batteries and Fuel Cells - Module IV 22-03-2024
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Intercalation Process
Process where lithium ions are reversibly removed or inserted into an
electrode without a significant structural change.
The positive material in a Li-ion cell is a metal oxide, with either a layered or
tunneled structure.
The graphitic carbon negative materials have a layered structure similar to
graphite.
When a Li-ion cell is charged, the positive material is oxidized and the
negative material is reduced.
In this process, lithium ions are de-intercalated from the positive material and
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MAUE602L – Battery and Fuel Cell
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Batteries and Fuel Cells - Module IV 22-03-2024
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MAUE602L – Battery and Fuel Cell
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Electrolytes
Four types of electrolytes have been used in Li-ion batteries:
Liquid electrolytes, Gel electrolytes, Polymer electrolytes and
Ceramic electrolytes.
Liquid electrolytes are solutions of a lithium salt in organic solvents,
typically carbonates.
Gel electrolyte is an ionically conductive material wherein a salt and
a solvent are dissolved or mixed with a high molecular weight
polymer.
Polymer electrolyte is a liquid- and solvent-free material, where an
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MAUE602L – Battery and Fuel Cell
Electrolyte Salts
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Electrolyte Solvents
A wide variety of solvents, including carbonates, ethers and acetates,
has been evaluated for non-aqueous electrolytes.
Carbonates offer excellent stability, good safety properties and
compatibility with electrode materials.
Neat carbonate solvents typically have intrinsic solution conductivity
and solvate lithium salts to high concentration.
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MAUE602L – Battery and Fuel Cell
Electrolyte Solvents
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Capacity Fade
SEI is not only built at the beginning of life (BOL) of the battery.
During deintercalation and intercalation of lithium, the electrode
particles suffer from volume changes and mechanical stresses.
The volume change is negligible for LiCoO2-based cathode materials
but can be up to 10% for graphite.
The dilation of the graphite particle surface causes the SEI to break.
This exposes fresh graphite surface on which new SEI is built.
Lithium is consumed continuously due to volume changes of the
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MAUE602L – Battery and Fuel Cell
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
The intercalation of lithium into the graphite particle layers follows a clear
staging mechanism.
In Stage IV, every fourth layer of the graphite structure is fully lithiated.
With further lithiation, Stage III is formed, which means that every third layer
is now lithiated.
The transition from Stage III to Stage II comes along with two additional
layers out of twelve being opened, whereas the final transition from Stage II
to Stage I requires six additional layers out of twelve to be opened.
Each time a new layer is opened, the graphite particle widens at the edge and
the SEI is expected to break.
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The SEI will cover the fresh surface, further depleting the available lithium.
Capacity loss is expected to be greatest in the range of Stage II when Stage I
is being opened
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Electrolyte Oxidation
Electrolyte oxidation (EO) tend to form on the cathode.
Keeping Li-ion at a voltage above 4.10V/cell while at an elevated
temperature promotes electrolyte oxidation.
This causes a permanent capacity loss and increases the internal
resistance.
No remedy exists to remove the layer once formed but electrolyte
additives lessen the impact.
Field observation shows that the combination of heat and high
voltage can stress Li-ion more than harsh cycling.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Dendrite Growth
A Li-ion battery operating under abnormal conditions, such as
overcharging or lower temperature charging, can lead to a harmful
phenomenon called lithium dendrite growth or lithium plating.
Lithium dendrites are metallic microstructures that form on the
negative electrode during the charging process.
Lithium dendrites are formed when extra lithium ions accumulate on
the anode surface and cannot be absorbed into the anode in time.
They can cause short circuits and lead to catastrophic failures and
even fires.
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MAUE602L – Battery and Fuel Cell
Dendrite Growth
The capacity loss is an accumulating effect along with the gradual
lithium dendrite growth.
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MAUE602L – Battery and Fuel Cell
At low rates (C/2), the LiCoO2 battery provided 1.67 Ah, and at
1.65 A (the 1 C rate) 1.60 Ah while at the C rate the average voltage
was 3.5 V.
LiMn2O4 provide 1.44 Ah at the C/5 rate (0.28 A)and 1.34 Ah at the
C rate (1.4 A), comparable to, but less than the capacity of C/LiCoO2
batteries.
For LiMn2O4 the discharge curves have a flat voltage profile with
average voltage at the C rate of 3.65 V, 0.15 V higher than C/LiCoO2
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MAUE602L – Battery and Fuel Cell
Initially, as the cells are charged at constant current, the state of charge
increases linearly while the cell voltage asymptotically approaches 4.2 V.
In the constant voltage portion of the charge, the current decays as the cell
approaches full charge.
Li-ion cells have high coulombic efficiency, typically 99.9%, and high
energy efficiency, typically 95 to 98%.
Because of the absence of parasitic processes, such as the gas forming
reactions common in aqueous systems, more complex charge
methodologies, such as pulse charging, can be employed.
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In these cells, lithium metal is plated onto the negative current collector
when the cell is charged.
The lithium plating-stripping process is efficient with this technology.
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