VLSI Design

Batteries and Fuel Cells - Module 1 17-01-2024
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MAUE602L – Battery and Fuel Cell
MAUE602L
Battery and Fuel Cell
Introduction to Course
Dr. T. Vijayakumar
Associate Professor / SMEC
Prof. Vijayakumar T
Module I – Introduction to Battery
Introduction
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Automotive Battery
 It provides electrical energy in the form of current to operate

the starter motor and ignition system while starting the
engine.
 Acts as voltage stabilizer, by supplying current for the lights,

and other electrical accessories when the alternator is not
handling the load.
Prof. Vijayakumar T
Course Modules
 Introduction – Electrochemistry
 Battery Performance and Selection
 Lead Acid Battery
 Lithium Ion Batteries
 Advanced Batteries for Electric Vehicles

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 Fuel Cells
 Types of Fuel Cells
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Course Outcomes
 Acquire and analyse the various type’s battery and Fuel cell.
 Characterize various Battery and Fuel cell performance.
 Maintain and inspect various Battery types and Fuel cell.
 Develop battery and fuel cell for the modern requirements.

Prof. Vijayakumar T
 Apply the advanced batteries for electric vehicles.
Text Books
 David Linden and Thomas B. Reddy ― Hand Book of Batteries

Third Edition, McGraw-Hill, NY, 2010
 Robert A. Huggins Advanced Batteries - Material Science Aspects,

Springer Publications, NY 2009
 D.A.J. Rand, P.T. Moseley,J. Garche , C.D. Parker, Valve Regulated

Lead Acid Batteries, Elsevier Publications, USA, 2004
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Module I
Introduction to Batteries
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Conditions for electron flow:

– Electrical Pressure – Battery or
Generator
– Conducting Path - Wires
Electron flow is from negative to

positive
Conventional current flow is assumed to

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be from positive to negative
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Effects of Current Flow

– Heat
– Magnetism
– Chemical effects
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Electrochemistry
 Electrochemistry is defined as the branch of chemistry that examines the

phenomena resulting from combined chemical and electrical effects.
 Chemical transformation, occurring due to the external applied electrical

current or leading to generation of electrical current is studied in
electrochemistry.
 A cell is the basic electrochemical unit providing a source of electrical

energy by direct conversion of chemical energy.
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 Electrochemical cell facilitates the transfer of electrons between two

different chemical species allowing for the production of electrical current.
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Electrochemical Cell
 An electrochemical cell typically consists of

 Two electronic conductors – Electrodes
 An ionic conductor – Electrolyte
 Electron conductor linking the electrodes – wires
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Battery
 Battery, composed of two or more cells, with each cell being independent
and contains all the chemicals and elements necessary to produce
electricity.
 Types of Cells
 Primary Cell
 Secondary Cell
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Primary Cells
 Primary cells cannot effectively be recharged.

 When their ability to supply current at the correct voltage is gone, they
must be replaced.
 Used in flashlights and radios.
 Primary cells can be further classified as either wet or dry.
 A wet cell is made up of two pieces of different metal that are placed in a
liquid.
 The dry cell is similar to the wet cell, but the electrolyte is a moist paste
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instead of a liquid.
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Secondary Cells
 Can effectively be recharged.

 Often referred as rechargeable batteries.
 Two chemical processes involved:
 one to discharge the cell
 one to charge the cell
 The charging system replaces the amperage used and brings the battery
back up to full potential.
 A car battery consists of a group of secondary cells.
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Cells Connected in Series

 By wiring the cells in series (positive to negative), we can increase the

voltage.
 Two cells that produce 1.5 volts each produce 3 volts.
 Four cells that produce 1.5 volts each produce 6 volts.
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Cells Connected in Parallel

 By wiring the cells in parallel (positive to positive and negative to

negative), the voltage will remain the same, but the ability of the cell to
produce current will be doubled.
 if we wire two cells in parallel, the amount of time the bulb will stay on
will be doubled while keeping the voltage the same.
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Gibbs Free Energy

 Gibbs free energy (G) is a thermodynamic potential that can be used to

calculate the maximum amount of work, other than pressure-volume
work, that may be performed by a thermodynamically closed system at
constant temperature and pressure.
ΔG = ΔH - T ΔS
 It also provides a necessary condition for processes such as chemical

reactions that may occur under these conditions.
 The Gibbs energy is minimized when a system reaches chemical
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equilibrium at constant pressure and temperature when not driven by an

applied electrolytic voltage.
 A reduction in G is necessary for a reaction to be spontaneous under
these conditions.
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Electrochemical Cell
 Types of Electrochemical Cell

 Galvanic Cell
 Electrolytic Cell
 Galvanic Cell
 Chemical reactions that result in the production of electrical energy
 Converts chemical potential energy into electrical energy
 Spontaneous redox reactions producing a flow of electrons
 G < 0
 Electrolytic Cell
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 Chemical changes occurs as a result of electrical current passage

 Driven by external source of electrical energy
 Non-spontaneous redox reactions
 G > 0
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Galvanic Cells
 Electrical energy is produced by a

chemical redox reaction.
 The classic example of a redox
reaction for a galvanic cell is the
reaction between aqueous solutions of
zinc (Zn) and copper (Cu)
 In this cell, the zinc is oxidized, and
the copper is reduced.
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Electrolytic Cells
 Electrolytic cells are composed of two half-cells: one is a reduction half-

cell, the other is an oxidation half-cell.
 Reduction takes place at the cathode and oxidation occurs at the anode.
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Electrodes
 An electrode is an electrical conductor used to make contact with a non-

metallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum
or air)
 Inert Electrodes do not react with the product produced or dissolved in
the electrolyte. Carbon and platinum are examples of inert electrodes.
 Reactive electrodes can react or dissolve in the electrolyte. Copper, Silver
and Mercury are examples of reactive electrodes
 The electrode at which the reaction of interest occurs is called the
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working electrode
 The electrode at which the other (coupled) reaction occurs is called the
counter electrode
 A third electrode, called the reference electrode may also be used
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Reactions
 At each electrode, an electrochemical reaction occurs. This reaction is

called a half cell reaction (since there are two electrodes in a typical cell
at which reactions occur)
 The overall chemical reaction of the cell is given by combining the two
individual half cell reactions
 There are two fundamental types of half cell reactions:
 Oxidation reactions
 Reduction reactions
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 A reaction is classified as oxidation or reduction depending on the

direction of electron transfer
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Reactions
 Oxidation
 Involves the loss of an electron
 Involves the transfer of electrons from the species to electrode
 Reduction
 Involves the gain of an electron
 Involves the transfer of electrons from the electrode to species
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Anode and Cathode

 The electrode at which electrons are lost is known as the anode, and the
one at which electrons are gained is the cathode
 At the anode: Oxidation, or loss of electrons, occurs.
 At the cathode: Reduction, or gain of electrons, occurs.
Reducing and Oxidizing Agents

 Reducing Agent
 Reduces a substance by giving electrons to it
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 Oxidizing Agent
 Oxidizes a substance by taking electrons from it
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Electrodes
Requirements of good electrode

 Good efficiency as a reducing or oxidising agent
 High coulombic output (Ah/g)
 Good conductivity
 Stability, ease of fabrication, and low cost.
 Hydrogen, Zinc, Lithium are good anode materials
 Oxygen, Metallic oxides, halogens are good cathode materials
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Electrolytes
 The electrolyte—the ionic conductor—provides the medium for transfer

of charge, as ions, inside the cell between the anode and cathode.
 The electrolyte is typically a liquid, such as water or other solvents, with
dissolved salts, acids, or alkalis to impart ionic conductivity.
 Some batteries use solid electrolytes like molten salt, which are ionic
conductors at the operating temperature of the cell.
 Must have good ionic conductivity but not be electronically conductive,
as this would cause internal short-circuiting.
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 Should be nonreactive with the electrode materials.
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Electrode Potential
 The major part of the ions released into the

solutions accumulate near the surface of
the electrode.
 As the distance from the surface of the
electrode increases, the concentration of
ions decreases and becomes equal to the
concentration in solution.
 As a result, the electrical double layer
(EDL) is formed.
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 Potential difference between the electrode

surface (o) and solution at distance x from
the electrode surface (x) is called
electrode potential (E)
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Electrode Potential
 The tendency of a metal ions to go into solution was measured by its

electrolytic solution pressure, Pe and its tendency to deposit from the
solution by its osmotic pressure, Po in the solution.
 Equilibrium was supposed to be reached when these opposing tendencies
balanced each other.
 If Pe > Po, then positive metal ions will pass into the solution. As a result
the metal is left with a negative charge, while the solution becomes
positively charged.
 If Pe < Po, then the ions will be deposited on the surface of the latter. This
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gives the metal a positive charge, while the solution is left with a negative
charge.
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Electrode Potential
 The value of electrode potential depends on the material of electrode, the

nature of the solvent, temperature, and concentration of the electrode
exchange ions.
 The electrode potential is measured by comparing with the reference
electrode potential.
Reference Electrode Potential
 Standard hydrogen electrode (SHE), whose potential is stable and is
assumed to be zero
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 The standard oxidation potential is equal in magnitude, but opposite in

sign to the standard reduction potential
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Electrode Potential
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Electrode Potential
 The difference in potential E° is given in units of volts (V).

 The more negative the E° value, the more readily the metal loses
electrons.
 The more negative the value, the stronger reducing agent the metal is.
 The more positive the E° value, the less readily the metal loses electrons,
and the more readily its ions pick them up again.
 The more positive the value, the stronger oxidising agent the metal ion is.
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Electrode Potential
 The electrode potential for a reaction is derived directly from the free
energy change for that reaction
 ΔG = - nFE
 n – no of moles of electrons involved in reaction
 F – Faradays Constant, 96485.32 C / mol
 E – Electrode potential due to chemical action, Volts
 The standard oxidation potential is equal in magnitude, but opposite in
sign to the standard reduction potential
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 ΔGcell = - nFEcell
 For any electrochemical cell, the potential is given by:
Ecell = Ereduction(cathode reaction) - Ereduction(anode reaction)
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Electrode Potential
 ΔGo = - nFEo, the Gibbs free energy at Standard Conditions
 This equation is called as Nernst Equation

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Electrode Potential
 Example illustrating Nernst Equation
 Oxidation takes place at the metal electrode and reduction takes place at
the hydrogen electrode
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Electrode Potential
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Electrode Potential
Consider Zn – Cu Electrochemical Cell

 The reaction with the lower standard reduction potential gets oxidized - the
other reaction proceeds as a reduction
Zn => Zn2+ + 2e E°red= - 0.7618 V
Cu2+ + 2e => Cu E°red= 0.341 V
 Thus, in the above example, Zn is oxidized, and Cu is reduced
 This is to ensure that ∆Gcell is negative (∆G = - NFE )
 This is why Zn got oxidized (and Cu reduced) in the above example.
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 In this case: Ecell = Eored (cathode) - Eored(anode) = 1.102 V.

 If the reverse were to occur, Ecell would be: -1.102 V, leading to a positive
∆Gcell
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Electrode Potential
 Activity (symbol a) is a measure of the “effective concentration” of a

species in a mixture, in the sense that the species' chemical potential
depends on the activity of a real solution in the same way that it would
depend on concentration for an ideal solution.
 Activity depends on temperature, pressure and composition of the
mixture.
 Note: for any metal present in the pure state, for any pure solid
compound, for a gas at 1 atm. pressure, and for water forming part of a
dilute solution, the activity is taken as unity.
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 The corresponding activity factors may then be omitted from the electrode
potential equation.
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Electrode Potential
Limitations of Nernst Equations

 In dilute solutions, the Nernst equation can be expressed directly in the
terms of concentrations (since activity coefficients are close to unity).
 At higher concentrations, the true activities of the ions must be used.
 Estimation of non-ideal activities of ions generally requires experimental
measurements.
 The Nernst equation also only applies when there is no net current flow
through the electrode.
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 The activity of ions at the electrode surface changes when there is current
flow, and there are additional overpotential and resistive loss terms which
contribute to the measured potential.
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Electrode Potential
Factors affecting Electrode Reaction Rate and Current

 Consider an overall reaction, O+ne  R (O dissolved oxidized species,
reduce to form R). In general, the current (or electrode reaction rate) is
governed by the rates of processes such as
 Mass transfer (e.g., of O from the bulk solution to the electrode surface)
 Electron transfer at the electrode surface
 Chemical reaction preceding or following the electron transfer.
 Other surface reactions, such as adsorption, desorption, or crystalization
(electrodeposition).
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 The rate constant for some of these processes (e.g. Electron transfer at
the electrode surface or adsorption) depend upon the potential.
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Overpotential in Electrochemical Cells

 Overpotential is the potential difference (or voltage measure) between a

theoretical or thermodynamically determined voltage and the actual
voltage under operating conditions.
 Ohmic drop
 Activation losses
 Concentration or Diffusion losses

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 Ohmic Drop
 Ohmic drop (IR) between electrodes results from the fact that the
electrolyte solution has finite conductivity.
 Contribution to polarization is equal to IR, where I is the current
density, and R is the resistance.
 The total internal impedance of a cell is the sum of
 The ionic resistance of the electrolyte (within the separator and
the porous electrodes)
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 The electronic resistances of the active mass, the current

collectors and electrical tabs of both electrodes
 The contact resistance between the active mass and the current
collector
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 Activation losses
 Activation polarization is caused by a slow electrode reaction. The reaction
at the electrode requires an activation energy in order to proceed.
 Activation overpotential at one or both electrodes arising from kinetic
inhibition of one of the steps involved in the electrode reaction.
 Concentration or Diffusion losses
 Diffusion overpotential at one or both electrodes due to the presence of
concentration gradients in the vicinity of the electrode surface.
 As a result of electrochemical reaction, the concentration at the electrode
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surface no longer have their equilibrium values.

 If migration through the electric double layer is very rapid, then diffusion
from the bulk of the solution towards the electrode will be unable to
replenish the ions at the double layer quickly enough and a concentration
gradient will result.
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Batteries and Fuel Cells - Module 1 17-01-2024

Module I – Introduction to Battery

Module I – Introduction to Battery

 It provides electrical energy in the form of current to operate

 Acts as voltage stabilizer, by supplying current for the lights,

Module I – Introduction to Battery

 Battery Performance and Selection

 Lead Acid Battery

 Lithium Ion Batteries

 Advanced Batteries for Electric Vehicles

 Types of Fuel Cells

Module I – Introduction to Battery

 Characterize various Battery and Fuel cell performance.

 Maintain and inspect various Battery types and Fuel cell.

 Develop battery and fuel cell for the modern requirements.

 Apply the advanced batteries for electric vehicles.

Module I – Introduction to Battery

 David Linden and Thomas B. Reddy ― Hand Book of Batteries

 Robert A. Huggins Advanced Batteries - Material Science Aspects,

 D.A.J. Rand, P.T. Moseley,J. Garche , C.D. Parker, Valve Regulated

Module I – Introduction to Battery

Module I – Introduction to Battery

Conditions for electron flow:

Electron flow is from negative to

Conventional current flow is assumed to

be from positive to negative

Module I – Introduction to Battery

Effects of Current Flow

Module I – Introduction to Battery

 Electrochemistry is defined as the branch of chemistry that examines the

 Chemical transformation, occurring due to the external applied electrical

 A cell is the basic electrochemical unit providing a source of electrical

 Electrochemical cell facilitates the transfer of electrons between two

Module I – Introduction to Battery

 An electrochemical cell typically consists of

Module I – Introduction to Battery

Module I – Introduction to Battery

 Primary cells cannot effectively be recharged.

Module I – Introduction to Battery

 Can effectively be recharged.

Module I – Introduction to Battery

Cells Connected in Series

 By wiring the cells in series (positive to negative), we can increase the

Module I – Introduction to Battery

Cells Connected in Parallel

 By wiring the cells in parallel (positive to positive and negative to

Module I – Introduction to Battery

Gibbs Free Energy

 Gibbs free energy (G) is a thermodynamic potential that can be used to

 It also provides a necessary condition for processes such as chemical

equilibrium at constant pressure and temperature when not driven by an

 Types of Electrochemical Cell

 Chemical changes occurs as a result of electrical current passage

Module I – Introduction to Battery

 Electrical energy is produced by a

Module I – Introduction to Battery

 Electrolytic cells are composed of two half-cells: one is a reduction half-

Module I – Introduction to Battery

 An electrode is an electrical conductor used to make contact with a non-

 At each electrode, an electrochemical reaction occurs. This reaction is

 A reaction is classified as oxidation or reduction depending on the

Module I – Introduction to Battery

Module I – Introduction to Battery