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Batteries and Fuel Cells - Module IV 22-03-2024

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MAUE602L – Battery and Fuel Cell

Module IV

Lithium Based Batteries


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium is the lightest metal


 Have higher electrochemical potential (3.027 V)
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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Batteries and Fuel Cells - Module IV 22-03-2024

Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

Lithium Metal Batteries


 Have high energy density
 Cycling produced unwanted dendrites on the anode. These growth
particles penetrate the separator and cause an electrical short.
 Lithium metal is also corrosive.
 The cell temperature would rise quickly and approach the melting point of
lithium, causing thermal runaway, also known as “venting with flame.”
 Lithium oxidizes very rapidly in air and water and therefore it is highly
flammable and slightly explosive when exposed to air and water.
Prof. Vijayakumar T

 Highly instable during charging process

Module IV – Lithium Ion Batteries

Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Two major types are used


 Lithium Ion
 Lithium Polymer
 Lithium Ion Batteries
 Li-ion batteries have a long cycle life and do not suffer from the high
self-discharge rate and memory effect of nickel-cadmium (NiCd) and
nickel metal hydride (NiMH) batteries.
 Charging efficiency is excellent, up to 99% for some Li-ion
chemistries.
Prof. Vijayakumar T

 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

Module IV – Lithium Ion Batteries

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Batteries and Fuel Cells - Module IV 22-03-2024

Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Battery


 Anode Plate – Graphite
 Cathode Plate– Graphite and Lithium alloy oxide
 Electrolyte – Lithium salt mixed in a liquid
 Li-ion batteries use a process known as intercalation, in which
lithium ions are incorporated into the structure of the electrode
materials.
 Polyethylene membranes are used to separate the plates inside the
cells.
Prof. Vijayakumar T

 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.

Module IV – Lithium Ion Batteries

Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

Lithium Ion - Construction


 Li-ion batteries are often constructed as.
 Cylindrical Cells
 Prismatic Cells
 Pouch Cells
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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”.

 The can is filled with liquid electrolyte, safety


disks are inserted into the top, and the electrodes
are welded to the outer battery terminals (in this
case, the top and bottom of the cell).
Prof. Vijayakumar T

 The cell is hermetically sealed by crimping the top


disk assembly closed.

Module IV – Lithium Ion Batteries

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.

 The electrode/separator assembly can be rolled, as with


cylindrical cells, or it can be a rectangular stack of
individual electrodes.

 The battery terminals can be placed as contact pads on


Prof. Vijayakumar T

the top or side of the housing.

 The prismatic cell thin form factor is well suited to use


in consumer electronics, particularly when ease of
battery replacement is desirable.
Module IV – Lithium Ion Batteries

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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.
Prof. Vijayakumar T

 By eliminating the rigid housing, pouch cells save on


cost, weight, and thickness.
 The flexible pouch is, however, prone to swelling and
this can pose problems with lifetime, capacity loss, and
safety.
Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Battery- Chemical Reactions


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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
Prof. Vijayakumar T

intercalated into the negative material.


 The reverse happens on discharge.

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

Positive Electrode Materials


 Positive electrode materials in commercially available Li-ion batteries
utilize a lithiated metal oxide as the active material.
 Requirements of positive electrode materials
 High free energy of reaction with lithium
 Can incorporate large quantities of lithium
 Reversibly incorporates lithium without structural change
 High lithium ion diffusivity
 Good electronic conductivity
Prof. Vijayakumar T

 Insoluble in the electrolyte


 Prepared from inexpensive reagents
 Low cost synthesis

Module IV – Lithium Ion Batteries

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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

Positive Electrode Materials


 Positive electrode materials can have one of two structure types (Layered
or Spinel).
 The structure types defines the amount of lithium that can be held by
electrodes
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Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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

 Positive Electrode Materials


 Lithium cobalt oxide (LCO)
 Lithium manganese oxide (LMO)
 Nickel cobalt aluminum (NCA)
 Lithium nickel manganese cobalt oxide (NMC, NCM)
 Lithium Iron Phosphate (LiFePO4)
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

Lithium Cobalt Oxide (LCO)


 Relatively short life span, low thermal stability and limited load capabilities
(specific power).
 Li-cobalt has a graphite anode that limits the cycle life by a changing solid
electrolyte interface (SEI), thickening on the anode and lithium plating while
fast charging and charging at low temperature.
 Li-cobalt should not be charged and discharged at a current higher than its
C-rating.
 This means that an 18650 cell with 2,400mAh can only be charged and
discharged at 2,400mA.
Prof. Vijayakumar T

 Forcing a fast charge or applying a load higher than 2,400mA causes


overheating and undue stress.
 For optimal fast charge, recommended C-rate is 0.8C or about 2,000mA.
* The capacity of a battery is commonly rated at 1C, meaning that a fully charged battery rated at
1Ah should provide 1A for one hour.
Module IV – Lithium Ion Batteries

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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

Lithium Manganese Oxide(LMO)


 Improved ion flow on the electrode, which results in lower internal resistance
and improved current handling.
 High thermal stability and enhanced safety, but the cycle and calendar life are
limited.
 Low internal cell resistance enables fast charging and high-current
discharging.
 In an 18650 package, Li-manganese can be discharged at currents of
20–30A with moderate heat build-up.
 It is also possible to apply one-second load pulses of up to 50A.
 A continuous high load at this current would cause heat build-up and the cell
Prof. Vijayakumar T

temperature cannot exceed 80°C (176°F).


 Li-manganese is used for power tools, medical instruments, as well as hybrid
and electric vehicles.

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

Nickel Cobalt Aluminum (NCA)


 Higher specific energy, reasonably good specific power and a long life span.
 Lesser safety and relatively higher cost.
 Like LCO, NCA batteries have lower thermal stability than competing
technologies.
 Their cost and cycle life also make them less attractive for off-grid products.
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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

Lithium nickel manganese cobalt oxide (NMC, NCM)


 Different blends of nickel, manganese, and cobalt are a successful and
promising approach for Li-ion batteries.
 The ratio of these three elements is sometimes listed in the electrode name –
an equal mix would have the chemical formula LiNi1/3Mn1/3Co1/3O2 and be
listed as NMC 1-1-1 or simply NMC 111.
 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
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specific applications including off-grid products.


 Can be tailored to serve as Energy Cells or Power Cells.
 Can be made to deliver up to 20A when designed as a power cells

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

Lithium Iron Phosphate (LiFePO4)


 LiFePO4 batteries exhibit qualities that make them ideally suited for off-
grid products where cost, safety, stability, and cycle life are primary
requirements.
 They have lower energy density than competing Li-ion chemistries and a
lower output voltage of 3.2V, but this is acceptable for most off-grid
applications.
 Many successful off-grid products use LiFePO4 batteries.
 Li-phosphate has a higher self-discharge than other Li-ion batteries,
which can cause balancing issues with aging
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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

Negative Electrode Materials


 Carbon electrodes offer stable morphology resulting in consistent safety
properties over their useful life.
 By utilizing low surface area carbons, electrodes with acceptable self-
heating rates may be fabricated.
 A wider variety of carbon types has been used in negative electrodes.
 Some cells utilize natural graphite, available at very low cost, while
others utilize hard carbons that offer capacities higher than possible with
graphitic materials.
 The structure of the carbon greatly influences its electrochemical
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properties, including lithium intercalation capacity and potential.

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

Negative Electrode Materials


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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

Additives in Negative Electrodes (Anode)


 Several additives have been tried, including silicon-based alloys, to enhance
the performance of the graphite anode.
 It takes six carbon (graphite) atoms to bind to a single lithium ion; a single
silicon atom can bind to four lithium ions.
 This means that the silicon anode could theoretically store over 10 times the
energy of graphite, but expansion of the anode during charge is a problem.
 Pure silicone anodes are therefore not practical and only 3–5 percent of
silicon is typically added to the anode of a silicon-based to achieve good
cycle life.
Prof. Vijayakumar T

 Using nano-structured lithium-titanate as an anode additive shows promising


cycle life, good load capabilities, excellent low-temperature performance and
superior safety, but the specific energy is low and the cost is high.

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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

 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
Prof. Vijayakumar T

ionically conducting phase is formed by dissolving a salt in a high


molecular weight polymer.
 Ceramic electrolytes refer to inorganic, solid-state materials that are
ionically conductive.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Electrolyte Salts
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Module IV – Lithium Ion Batteries

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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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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Electrolyte Solvents
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Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Solid Electrolyte Interface


 A small layer that builds up on the anode is the solid electrolyte
interface (SEI).
 SEI is an electrical insulation but has sufficient ionic conductivity to
allow the battery to function normally.
 While the SEI layer lowers the capacity, it also protects the battery
and increases its longevity.
 The SEI layer develops as part of a formation process and an
improper formation can cause permanent capacity loss and a rise in
internal resistance.
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 The process includes several cycles, float charges at elevated


temperatures and rest periods that can take many weeks to complete.
 High self-discharge hints to impurity as part of a potential
manufacturing defect.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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MAUE602L – Battery and Fuel Cell
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Module IV – Lithium Ion Batteries

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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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particle surface during operation and the cell progressively loses


capacity.

Module IV – Lithium Ion Batteries

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Batteries and Fuel Cells - Module IV 22-03-2024

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MAUE602L – Battery and Fuel Cell
Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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

Module IV – Lithium Ion Batteries

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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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 Capacity fade is another potential hazard of lithium dendrite growth.


 The lithium dendrite reacts with the electrolyte, causing it to
decompose and triggering the loss of active lithium inside the battery.

Module IV – Lithium Ion Batteries

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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

 Dendrite Growth
 The capacity loss is an accumulating effect along with the gradual
lithium dendrite growth.
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Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 An ideal SEI layer should be


 Thin and compact to minimize the consumption of lithium and
reduce the transport resistance
 Uniform in morphology and structure to ensure the homogenous
ionic conduction;
 Electrochemically stable to avoid iterative buildup and breakdown
 Mechanically flexible to withstand the large volume changes of
active materials without delamination
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Module IV – Lithium Ion Batteries

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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

 Factors affecting SEI layer


 Electrolyte - Modifying the components gives rise to significant changes in
the SEI characteristics.
 Salts, solvents, and additives all have large impacts on the morphology,
composition, homogeneity, and mechanical properties of SEI films.
 Temperature - Influences the reduction kinetics of electrolytes on the
electrode surface, resulting in different components and nanostructures of
SEI layers
 Current density - affects the quality of SEI formed as it determines the
diffusion rate of molecules and ions.
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 Electrode materials - with different Li-storage mechanisms, polymorphs,


lattice facets, and electronic properties may result in distinct SEI layers
 Graphite electrode shows stable volume change(10%) where as Silicon and
Tin shows significant volume change leading to forming and breaking of
SEI layers
Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Effect of carbon type


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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

 Lithium Ion Performance – Discharge Rate Capability


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Discharge Rate Capability


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Discharge Rate Capability

 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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cells at the C rate.

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Discharge Rate (Constant Power)


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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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

 Lithium Ion Performance – Discharge Rate (Constant Power)


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Discharge Rate Constant Power

 At 1 W the C/LiCoO2 battery provided 6.3 Wh, or 145 Wh/kg and


380 Wh/L.

 At 1 W the C/LiMn2O4 battery provided 5.5 Wh, or 130 Wh/kg and


332 Wh/L.
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Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Discharge Rate (Various Models)


Prof. Vijayakumar T

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Effect of Temperature


 Diffusion Rate – Higher temperatures leads to faster diffusion rate of
lithium ion due to increased kinetic energy
 SEI Layer – Optimal SEI layer forms within a specific temperature
ranges. Excessive temperatures may affect the SEI layers
 Electrolytic Conductivity – Higher temperatures increases the
electrolytic conductivity. Excessive temperature can lead to Lithium
decomposition and thermal runaway
 Phase Transition – Temperature induced phase transition can impact
the intercalation process and could degrade performances
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 Thermal Stability – Excessive temperature can accelerate electrolyte


degradation reactions, electrode corrosion and SEI breaking leading to
capacity losses.

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Effect of Temperature


Prof. Vijayakumar T

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Effect of Temperature


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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Effect of Temperature


 Comparing the C/LiMn2O4 and C/LiCoO2 batteries, the spinel product
provides nominally 0.25 V higher voltage
 C/LiCoO2 product provides typically 20% more coulombic capacity at
any given temperature than the C/LiMn2O4 unit.
 Between -10°C and 60°C, the C/LiMn2O4 18650 battery delivered 1.4
Ah with an average voltage of 3.9 V above 20 ° C, and 3.7 V at
-10 °C.
 At -20°C, the C/LiMn2O4 product provided 1.3 Ah at 3.5 V, on
average.
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 C/LiCoO2 batteries provided similar capacities over the range of


temperatures evaluated.
 At or above -10°C, the battery provided 1.6 Ah and 1.5 Ah at -20°C.
The average voltage at 21°C was 3.6 V, and at -20°C, 3.2 V.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Effect of Temperature (high discharge rate)


Prof. Vijayakumar T

Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Capacity and Energy


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Module IV – Lithium Ion Batteries

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Capacity and Energy


 C/LiCoO2 battery show higher capacity and energy than the
C/LiMn2O4.
 Because of the higher voltage of the C/LiMn2O4 product, the energy
difference is less than the capacity difference at any given temperature.
 As shown, the batteries offer consistent capacity and energy between
0°C and 60°C, and 90% of the 21°C capacity at -20°C.
 The average cell voltage is depressed significantly at the lower
temperature
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Cycle Life


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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Cycle Life


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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Cycle Life


 For Cobalt based battery the fade rate in all cases was comparable and
relatively linear. After 500 cycles, the battery cycled at the 1C rate at 21°C
delivered 1.42 Ah, 91% of the initial value, and the one cycled at 45°C at
the 1C rate delivered 1.35 Ah on the 500th cycle, or 87% of the initial
value.
 For Manganese based cell, after 500 cycles at the 1C rate, the battery
delivered 1.01 Ah, or 70% of the initial capacity. The cell cycled at the
0.5C rate at 21°C delivered 1.16 Ah after 500 cycles, or 80% of its initial
capacity.
 Higher fade rates are observed at 45°C.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Cycle Life


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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Cycle Life


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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Cycle Life


 As batteries are cycled their impedance increases, resulting in reduced
voltage and lower delivered energy.
 For both the battery cycled at the 1C rate at 21°C the battery voltage
decreased by typically 0.3 mV/cycle.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Self Discharge


 Side Reactions
 During storage or idle periods, reactions between the electrolyte
and electrode surfaces can form solid electrolyte interface (SEI)
layers, which consume lithium ions and reduce the battery's
capacity over time.
 Parasitic Currents
 Internal parasitic currents, also known as leakage currents or self-
discharge currents, flow within the battery even when it is not
actively supplying power to an external load.
Prof. Vijayakumar T

 These currents arise from electrochemical processes, such as ion


diffusion and chemical reactions, occurring within the battery's
components.
 Parasitic currents contribute to the gradual depletion of the
battery's stored charge.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Self Discharge


 Ion Migration
 Over time, lithium ions may migrate within the battery due to
concentration gradients and diffusion processes.
 Result in the redistribution of charge and the loss of capacity as
lithium ions move away from the active electrode materials and
become trapped in inactive regions of the battery.
 Passive Components
 Components such as the separator and current collectors within
the battery can contribute to self-discharge through their inherent
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electrical resistance and capacitance.


 These passive components may facilitate the flow of small
leakage currents or promote side reactions that lead to charge loss
over time.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Self Discharge


 Temperature Effects
 Temperature fluctuations can exacerbate self-discharge by
accelerating side reactions and ion migration processes within the
battery.
 Higher temperatures increase the rate of chemical reactions and
diffusion kinetics, leading to faster degradation and discharge of
the battery's stored energy.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Storage Performance


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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Performance – Storage Performance (Temp Effect)


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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Lithium Ion Battery Charging


 Typical charging voltage – 4.2 Volts
 Cells should be charged with constant voltage
 Charging current should change in response to the cell voltage.
 Higher density are more dangerous
 Careful attention should be given when connecting Li-Ion cells to
form a battery pack.
 If the connected cells do not have the same output and capacity, the
battery pack can be overcharged and may cause fire.
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 Expensive to produce due to the required protection circuit.


 The cycling of the battery must be monitored, due to the explosive
nature of the battery.

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MAUE602L – Battery and Fuel Cell
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
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Lithium-Based Batteries
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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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Prof. Vijayakumar T

*charging to higher voltages must be controlled to avoid lithium plating on the


negative electrode, particularly at lower temperatures to improve cycle life
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Li-ion cells are degraded irreversibly by overcharge or over-discharge,


and may vent if overcharged.
 Li-ion batteries typically employ battery management circuitry to ensure
safe operation and prevent overcharge.
 The protection circuit limits the peak voltage of each cell during charging
and prevents the voltage from dropping too low during discharge.
 The temperature of the battery is also monitored during the cycling
activity.
 The circuit also contains electronics and fuses to prevent polarity reversal.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell
Prof. Vijayakumar T

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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Thin film Solid State Li-ion battery


 A specialized type of Li-ion battery developed for semi-conductor
and printed circuit board (PCB) applications are thin-film, solid-state
devices.
 Employ ceramic negative, solid electrolyte and positive electrode
materials, can sustain high temperatures (250°C)
 Can be fabricated by high volume manufacturing techniques on
silicon wafers.
 Batteries of this type can be very small, 0.04 cm x 0.04 cm x 2.0 µm.
 Cells with liquid or polymer electrolytes cannot sustain these
Prof. Vijayakumar T

conditions because of the volatility or thermal stability of organic


components.
 Cells that employ lithium metal also fail as solder re-flow conditions
exceed the melting point of lithium
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MAUE602L – Battery and Fuel Cell
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Thin film Solid State Li-ion battery


 These cells are fabricated by sequential layer deposition of the cell
components using RF magnetron sputtering.
 The metallic current collector components are deposited by DC
magnetron sputtering.
 The cells are fabricated on a substrate, typically alumina, quartz, soda-
lime glass, or silicon.
 Positive current collectors of gold or platinum (0.1 µm to 0.3 µm), over
a layer of cobalt (0.01 µm to 0.05 µm, to improve adhesion), have been
used.
Prof. Vijayakumar T

 Cells using either LiCoO2 or LiMn2O4 positive electrode materials have


been fabricated.
 The positive electrode layer of laboratory test cells is typically 0.05 µm
to 5 µm thick and 0.04 cm2 to 25 cm2 in area, depending on the
capacity required by the application.
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Lithium-Based Batteries
MAUE602L – Battery and Fuel Cell

 Thin film Solid State Li-ion battery


 The electrolyte layer, LiPON, is typically 0.7µm to 2 µm thick.
 Cells with and without negative electrode materials have been
fabricated.
 To accommodate the difference in volumetric capacity of positive and
negative electrode materials, the thickness of the negative electrode is
typically 7% of the positive electrode.
 Negative current collectors of copper, titanium, or titanium nitride (0.1
µm to 0.3 µm) are typical.
 Alternatively, the negative electrode materials may be omitted.
Prof. Vijayakumar T

 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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