Electrochemical energy systems

Batteries

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 An Electrochemical cell

• An electrochemical cell is a device in which a

redox reaction is utilized to get electrical energy.
• Commonly referred to as voltaic or galvanic cell.
• The electrode where oxidation occurs is called
anode while the electrode where reduction
occurs is called cathode.

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 Electrochemical cell or galvanic cell
• A device used to convert the chemical energy produced in a redox reaction to
electrical energy is called an electrochemical cell or chemical cell.
• Depending upon the changes occuring in the electrochemical cell , these can
be of two types electrolytic cell and galvanic or voltaic Voltages generated by
such cells have been referred to as electromotive force.

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 Nernst equation
The Nernst equation is used to calculate the voltage of an electrochemical cell or to
find the concentration of one of the components of the cell.

T = temperature (K)
n = number of moles of electrons exchanged in the electrochemical reaction (mol)
F = Faraday's constant, 96500 coulombs/mol
R = Universal gas constant, R = 8.314 472(15) J K−1 mol−1

From the above equation,

The electrode potential is directly proportional to
(i) the concentration of the solution and
(ii) the temperature of the solution
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 Batteries
• Batteries use a chemical reaction to do work on charge and produce
a voltage between their output terminals.
• The basic element in a battery is called an electrochemical cell and
makes use of an oxidation/reduction reaction.

• An electrochemical cell which produces an external current is called

a voltaic cell. Voltages generated by such cells have historically been
referred to as emf (electromotive force).

• Batteries are devices where several electrochemical systems are

connected together in series.
• And can store chemical energy for later release as electricity

• It is a source of direct electric current at a constant voltage.

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Cell vs. Battery:
•A cell is the basic electrochemical unit providing a source of
electrical energy by direct conversion of chemical energy.
•The cell consists of an assembly of electrodes, separators,
electrolyte, container and terminals.
•A battery consists of one or more electrochemical cells, electrically
connected in an appropriate series/parallel arrangement to provide
the required operating voltage and current levels.

Characteristics of Batteries:
1. Nominal and operating voltage
2. Capacity
3. Self Discharge
4. Depth of Discharge

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Nominal voltage :
The nominal voltage of a cell is the potential difference between the positive and negative
electrodes in fully charged condition (secondary) or freshly prepared condition (primary).
Eg. Nominal voltage of dry cell : 1.5 V
Nominal voltage of lead‐acid cell : 2.0 V

Operating voltage :
•o The sustained voltage that the cell can maintain during discharge at a particular current
is the operating voltage before reaching the cut‐off voltage .
Eg. While discharging, the operating voltage of a dry cell for a typical discharge duration
lasting 20 hours will be of the order of 1.2 V
•When the voltage falls below this, the battery is assumed to be dead (it can no longer be
capable of taking any load).

•The end voltage, or cutoff voltage (COV), is defined as a point along the discharge curve
below which no usable energy can be drawn for the specified application.

•Typically 0.9 V has been found to be the COV for a 1.5‐V cell when used in a flashlight.

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Capacity :
A battery's capacity is the amount of electric charge it can deliver at the rated
voltage.
The more electrode material contained in the cell, the greater its capacity.

The capacity of the cell = discharge current x discharge duration in hours during which the
cell will maintain voltage above a specified terminal voltage (above the specified cut off
voltage)

Capacity is measured in units such as ampere hours (Ah).

Eg. If a lead‐acid cell is discharged at a current of 5 amperes and it lasts for 10

hours before reaching the cut‐off voltage, then the capacity of the cell is
5 amp. x 10 hours = 50 Ah

A small cell has less capacity than a larger cell with the same chemistry, although
they develop the same open‐circuit voltage.

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Self discharge:
o The loss in capacity of a cell when stored at specified temperature conditions
without actually discharging, is called self discharge.

o This is estimated by storing the cell at the specified temp. (eg.25oC for 1 year) and
then discharged to check the residual capacity.

Percentage of self discharge = capacity after storage x 100

capacity before storage

For an ideal cell (battery), the self discharge should be low.

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Depth of discharge (DOD):
o DOD, is used to describe how deeply the battery is discharged.
o If we say a battery is 100% fully charged, it means the DOD of this
battery is 0%,
o If we say the battery have delivered 30% of its energy, here are
70% energy reserved, we say the DOD of this battery is 30%.
o And if a battery is 100% empty, the DOD of this battery is 100%.
o DOD always can be treated as how much energy that the
battery has delivered.

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 Types of batteries
• Primary battery (Primary cells)
cells in which the cell reaction is not
reversible. When all the reactants have been converted to product,
no more electricity is produced and the battery is dead.

• Secondary battery (secondary cells) in which cell reactions can be

reversed by passing electric current in the opposite direction. Thus
it can be used for a large number of cycles.

• Flow battery and fuel cell in which materials (reactants, products,

electrolytes) pass through the battery, which is simply an
electrochemical cell that converts chemical to electrical energy.

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 Primary batteries

• Dry or lachlanche cell

• Alkaline battery
• Lithium batteries

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DRY(or LACLANCHE) CELL

• The venerable
carbon-zinc cell
or Lechlanche' cell
was invented in
1866 by Georges
lachlanche and was
the most common
small battery
throughout most of
the 20th century

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• Dry cell contains Zn, NH4Cl, ZnCl2 and MnO2

• Anodic reaction
• Zn(s) -> Zn2+(aq) + 2e-

• Cathodic reaction
• H2O + 2MnO2(s) + 2e- -> Mn2O3(s) + 2OH-

• Some of the complexity of this reaction comes from the fact that the reduction
of the ammonium ion produces two gaseous products

• 2NH4+(aq) + 2OH- -> 2NH3(g) + H2O(g)

which must be absorbed to prevent the buildup of gas pressure.

• ZnCl2 (aq) + 2NH3 (g) -> Zn(NH3)2Cl2 (s)

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 Applications
• Used in flash lights, transistor radios, calculators etc

Disadvantages of dry cell

• The voltage of this cell is initially about 1.5 volts, but decreases as
energy is taken from the cell. Due to the accumulation of the
products on electrodes. It also has a short shelf life and
deteriorates rapidly in cold weather.

• Oxidation of the zinc wall eventually causes the contents to leak

out, so such batteries should not be left in electric equipment for
long periods.

• While these batteries have a long history of usefulness, they are

declining in application since some of their problems are overcome
in ALKALINE BATTERIES.
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 ALKALINE DRY CELLS

• Alkaline cells overcome some of the problems

with carbon-zinc batteries by using potassium
hydroxide in place of ammonium chloride in the
electrolyte.

• Potassium hydroxide is a base or alkaline material,

hence "alkaline" batteries. The active materials
used are the same as in the Leclanché cell – zinc
and manganese dioxide.
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 Chemistry

• The zinc anode does not form the container; it is in the form of a
powder instead, giving a large surface area. The following half-cell
reactions take place inside the cell:

• At the anode: Zn + 2OH – → Zn(OH)2 + 2e–

• At the cathode:
2MnO2 + H2 O + 2e – → Mn2 O3 + 2OH –

• Overall: Zn + 2MnO2 + H2 O → Zn(OH)2 + Mn2 O3

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 Advantages and Uses

• Zinc does not dissolve as readily in alkaline

medium
• Long life
• Used in calculators and watches

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Lithium batteries

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 Lithium batteries
• Lithium is the most electronegative metal in the
electrochemical series.

• Due to its position and low density, it offers, as an anode,

the highest amount of electrical energy per unit weight
among all solid elements.

• Li cannot be used with aqueous electrolytes due to the

very vigorous corrosive reaction between Li and water
with flammable hydrogen as the product.

• Hence, Li cells are generally properly sealed against

contact with air and moisture.

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Lithium primary cells are divided into two types:
(i) Lithium primary cells with solid cathodes
Eg: Li-MnO2 cells and Li-iodine cells
(ii) Lithium primary cells with liquid cathodes
Eg: Li-SO2 cells and Li-SOCl2 cells
Lithium acts as an anode with the organic electrolytic
solvents like propylene carbonate ether, tetrahydrofuran,
dioxalone, dimethoxy ethane.
Some of the lithium salts like Lithium perchlorate, lithium
tetrafluoroborate, lithium tetrafluorophosphate also act as
good electrolytes.
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Li/MnO2 Cell: (Cylindrical and coin cells)
Lithum anode with pure MnO2 as the solid cathode
material in a Li salt solution in organic solvent as an
electrolyte has an e.m.f. of 3 volts.
Cell Reaction:
Li Li+ + e- (Anode Reaction)
nLi+ + ne- + MnO2 LinMnO2 (Cathode reaction)

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 Chemistry
• The cell is represented as
• Li/Li+(nonaqueous KOH(paste) / MnO2,Mn(OH)2,C.

• The anode is lithium.

• The cathode is carbon in contact with manganese (III),
Manganese(IV) electrode.
• The electrolyte is a paste of aqueous KOH

• At anode
Li --- Li+ + e-
• At cathode
MnO2+2H2O+ e- --- Mn(OH)2 + OH-

• The overall reaction is

• Li + MnO2+ 2H2O -- Li + + Mn(OH)3 + OH-
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 Advantages and uses

• High electron density

• Long shelf life
• Low self discharge
• Need less maintenance
• Can provide very high current
Uses
• Used in auto focus cameras, calculators
etc
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• Li/Iodine Cell: Has Li as anode, Iodine - poly(2-vinyl pyridine)
complex as cathode and a Lithium salt as the electrolyte. E.m.f. 2.4
– 2.8 V. Highly stable and is used in many electronic equipments.
• Li/SOCl2 : e.m.f. 3.3 - 3.6V
Cell Reaction: 4Li + 2SOCl2 LiCl + S + SO2
Advantages: High Energy density; long shelf life.
Disadvantages: Only low to moderate rate applications.
Uses:Memory devices; standby electrical power devices
• Li/SO2 e.m.f. 3.00V
Cathode: 50% SO2 with solvent acetonitrile or propylene carbonate
or both
• Cell Reaction: 2Li + 2SO2 Li2S2O4
Advantages: High energy density; best low-temperature performance;
long shelf life.
Disadvantage : High-cost
Application: Military and special industrial needs 26