MODULE 2

ENERGY SOURCES, CONVERSION AND STORAGE

INTRODUCTION
Batteries are needed for various uses and different applications require batteries with
different properties. The battery required to start a car must be capable of delivering a large
electrical current for a short span of time. The battery that powers a cardiac pacemaker must
be small, rugged, leak proof, compact and capable of delivering a steady current for an extended
period of time. In UPS systems, longer and consistent backup is needed. Hearing aid batteries
must small, whereas batteries for torpedoes and submarines must be stable during storage and
render high power for short periods & certainly rechargeable. For a lap-top computer, a battery
in the form of a flexible sheet distributed around the case is much preferred. Batteries remain
an enormous industry with a turnover of billions of pounds worldwide.

BASIC TERMS AND TERMINOLOGIES:

Battery: Battery is a small chemical device that converts chemical energy into electrical energy
when required. Alternatively, it can be defined as a reactor that stores chemical energy that can
act as a source of direct current on demand.
Cell & Battery: A cell is a single arrangement of two electrodes and an electrolyte capable of
providing electricity due to redox reaction/ free energy change within the cell. Battery is a
combination of two or more electrochemical cells arranged in series or parallel to produce
higher voltages.
Charging: It is a process wherein the battery is reestablished to its original charged condition
by reversing the current flow.
Discharging: It is a process in which a battery supplies electrical energy to an external device.
Separator: It is a physical barrier between anodes & cathodes in a battery to prevent internal
short circuiting. Separators must be ionically conducting but electronically insulating and inert
in the battery environment.
Fuel cell: The fuel and the oxidizer are supplied to the cell continuously while it is operating
to generate electricity.
Voltage: Voltage can be defined as the amount of pressure of electrons that pass from a negative
electrode to a positive electrode. Mathematically,
Voltage (V) = Current (I) × Resistance (R)
Current: It is a measure of the rate at which the battery is discharging.
Capacity: It is the charge or the amount of electricity that may be obtained from the battery
and is given in ampere hours (Ah).
Electricity storage density: Electrical storage density is capacity per unit weight (amount of
electricity per unit weight) of the battery.
Power density: Power generated per unit weight of the battery.
Energy density: Measure of available energy per unit weight of the battery.
Cycle life: Primary batteries are designed for single discharge, but a secondary battery is
rechargeable. The number of complete charge to discharge cycles a battery can perform before
its capacity fails below 80% of its initial capacity is termed as cycle life.
Shelf life: It is the time an inactive battery can be stored before it becomes unusable i.e ,the
length of time a battery can remain without losing its energy capacity
Design life: It is the time passed before a battery becomes dead whether it is in active use or
inactive.

CLASSIFICATION OF COMMERCIAL CELLS

Primary Cells: They are galvanic cells which produce electricity from chemicals that are
sealed into it when it is made. This type of cells cannot be recharged as the cell reaction cannot
be reversed efficiently by recharging. Once the cell reaction has reached equilibrium the cell
must be discarded. The battery is said to be „dead‟ when it cannot generate any more
electricity.
These are also known as „throw – away‟ batteries or irreversible batteries.
Eg: Dry cell, Lithium copper sulfide cell
Secondary cells: A secondary cell is rechargeable by passing current through it. During the
process of charging, an external d.c supply reestablishes a non- equilibrium mixture of reactants
by reversing the spontaneous cell reaction. Now, the cell can be used for supplying current
when required, as the reaction sinks toward equilibrium again. Thus a secondary cell can be
used through multiple cycles of discharging and charging. Such cells are also known as
rechargeable cells, storage cells, or accumulators.
Eg. Lead-acid batteries, Nickel-cadmium cell, Lithium- ion battery
Differences between Primary and Secondary batteries

Primary Batteries Secondary Batteries

1.Cell reaction is irreversible Cell reaction is reversible
2. They must be discarded after its They may be recharged a number of
active elements have been consumed times from an external d.c. source
during its useful life

3. Have relatively short shelf life Have very long shelf life
4. Function only as galvanic cells Function as galvanic cells during
discharge & as electrolytic cells
during charging process.

5. Cannot be used as energy storage Can be used as energy storage

devices devices (e.g. solar/ thermal energy
converted to electrical energy)

6. Cannot be recharged Can be recharged.

e.g. Dry cell, Li-MnO2 battery e.g.Lead acid battery, Ni-cd battery

LITHIUM BATTERIES:
Utility of Lithium in batteries is due to following reasons
* Light weight
* Low electrode potential (SRP)
* Good conductivity
* High energy density

LITHIUM PRIMARY BATTERY:

Lithium thionyl chloride battery:
Anode: Lithiunm
Cathode: Carbon
Electrolyte: Non aqueous thionyl chloride ( SOCl2 / LiAlCl4)
Thionyl chloride acts both as electrolyte and active cathode material
 As seen above, anode is lithium foil which is pressed against the inner wall of a stainless
steel or nickel plated can. The separator is made of non-woven glass. The cylindrical, highly
porous cathode which take up most of the cell volume is made of Teflon-bonded carbon black.
The electrolyte is absorbed in the porous cathode.

Reactions:
At the anode: At the anode: Li → Li+ + e
Li+ + Cl- → LiCl
Li + Cl- → LiCl +e

At the cathode: 2SOCl2 + 4e → S + SO2 + 4Cl-

Net reaction: 4Li + 2SOCl2 → 4LiCl + S + SO2

Applications:
• As a power source for instruments and small electronics
• Military applications where high energy density is need
LITHIUM SECONDARY BATTERY: LITHIUM ION CELLS
Lithium metal cannot be used safely in secondary batteries. Hence, various lithium
compounds have been made, which are used in rechargeable batteries, commonly known as
Lithium –Ion Cells. In these type of batteries, lithiated metal oxide such as LiCoO2, LiV2O5,
LiMn2O4 etc are inserted into the cathode which consists of a layered graphite crystal. The
electrolyte is normally LiPF6, but LiBF4 can also be used as LiPF6 is not corrosion resistant.

Construction:
Construction:
Anode: Lithium intercalated graphite/carbon, metal matrix composite or polymer.
(Anode current collector: Copper foil)
Cathode: Partially lithiated oxides of Co, or Mn. ( LiyCoO2, LiyMn2O4)
(Cathode current collector: Aluminum foil).
Separators: polyolefin’s using 3 to 8μm layers with 50% porosity.
[Serves as a safety device by closing off the pores through which ions travel (shunt current.)]
Electrolyte: The electrolyte is usually a 1-molar solution of a lithium salt in an organic solvent.
Ex: 1) Lithium hexafluorophosphate (LiPF6) in the solvent
propylene carbonate
2)Lithium tetrafluoroborate (LiBF4) in the solvent ethylene carbonate

Schematic diagram of Rechargeable lithium ion battery

Working:
Lithium is intercalated between the layers of graphite to form Lithium-Graphite
intercalated compound (GIC). It is prepared by electrochemically reducing graphite (has a
layered structure) in an aprotic organic electrolyte containing lithium salts. Li-GIC undergoes
oxidation leaving an electron.
At anode: LixC6 xLi+(solv) + 6C(s) + xe (1)
During discharging reaction, lithium is deintercalated from lithiated graphite (negative
electrode) and lithium ions dissolve into the electrolyte. The amount of lithium present in the
LiCoO2 electrode deviates reversibly during charge and discharge as follows:
At cathode: Li (1-x) CoO2(s) + xLi+ (solv) + xe- LixCoO2(s) (2)
Net cell reaction:
LixC6 + Li (1-x) CoO2(s) Discharge LiCoO2(s) + 6C (3)
Charge
Explanation:
During cell discharge, the lithium ions are extracted as presented in half-reaction (1).
Cobalt dioxide serves as cathode and the reduction half reaction during discharge is shown in
eq. (2), where cobalt undergoes reduction from IV to III oxidation state. The overall reaction
is shown in eq. (3).
During discharge the Li+ ions spontaneously move from the lithium graphite anode to
the CoO2 cathode enabling current to flow through the external circuit and the battery delivers
energy to the external load. When charged, it receives energy from a d.c. power source and
cobalt ions are oxidized, and lithium ions migrate into the graphite. Thus, the electrode that
functions as anode during discharging process becomes a cathode while its charged.
 Lithium-ion batteries thus operate based on what is sometimes called the "rocking
chair" or "swing" effect. This involves the transfer of lithium ions back and forth between the
two electrodes. Hence called lithium rocking chair or swing batteries. Both the anode and
cathode are materials into which, and from which, lithium can migrate. During insertion (or
intercalation) lithium moves into the electrode. During the reverse process, extraction (or
deintercalation) lithium moves back out.

Applications:
• Lithium-ion batteries are mainly used in applications such as mobile telephones and
computing devices where one or more of the advantages like size, weight or energy is
central than the additional cost.
• Lithium-ion-polymer batteries need to be used when the battery design matters in a
particular application as different designs such as Cylindrical, jelly-roll design, flat
rectangular are possible.
• It is used in current-generation laptops, cellular phones, video-recorders.
• It is also used in portable CD players, televisions and implantable medical devices.

Advantages:
• The design of lithium-ion batteries helps to overcome the safety risks related to the
extremely reactive properties of lithium metal.
• Long cycle life (400-1200 cycles).
• They are lighter, smaller and offer more energy density compared to nickel-cadmium
or nickel-metal-hydride batteries
• They can be operated in a wide range of temperature.
Disadvantages:
• Poor charge retention.
• The self discharge rate is about 10% per month.
• It prices is high compared to other types of cells commonly used.