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History of Electrochemistry
History of Electrochemistry
History of Electrochemistry
It was in the sixteenth century when the new phenomenon of electricity was growing, the
electrochemistry took a birth by the Italian physician and anatomist Luigi Galvani ( 1737-
1798). In 1791 Galvani proposed animal electricity. He demonstrated that animal tissue
contained an unknown vital force, which activated nerves and muscles when touched with
metal probes.
Later in the nineteenth century the foundation stone of modern electrochemistry goes to
Alessandro Volta (1745-1827), a professor of natural philosophy at the University of Pavia,
who showed in the early 1800s that the frog legs used in Galvani' s experiments served only
as an electroscope and suggested that the true source of stimulation was the contact
between dissimilar metals. He effectively demonstrated the first electrochemical battery.
Michae.l Faraday ( 1791-1867) is considered to be one of the greatest scientists in history.
Some refer to him as the greatest experimentalist ever, especially because his work on
electricity found expression in day-today technology. Farad, the Sl unit of capacitance, and
the Faraday constant, are named after him.
The momentous period for the growth of electrochemistry was marked by the American
Scientist Josiah Willard Gibbs (1839-1903) in the latter half of the nineteenth century. In
fact he was the first awardees of doctoral degree for an engineering thesis by Yale University.
In 1836, John Frederic Daniell ( 1790-1845) unveiled a two-fluid battery, which was the
l first battery to provided constant and reliable source of current over a long period of time.
\ In 1888, Walther Hermann Nernst (1864-1941) came out with a theory connecting the
l
i electromotive force (EMF) in an electrochemical cell to the free energy of the chemical
l reaction that produces the current. He formulated the well known Nernst equation. He also
I demonstrated that solvents with high dielectric constants promoted the ionization of
I
'
substances.
j
~ ... A
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
4 Engineering Chemistr
Electrochemistry today has matured into a multidisciplinary branch of study. It is now used
in much fundamental research, such as the study of new organic and inorganic compounds
and biological systems. In more applied research areas, such as used to shape materials
from the macroscopic to the microscopic scale, to understand and prevent the corrosion of
materials at low and extremely high temperatures, to probe the function of living cells, and
to convert chemical energy into electricity. More recently the introduction of in-situ scanning
probe t~chniques has allowed us to follow electrochemical reactions on an atomic or molecular
scale.
Electrocheinical cells
Electrochemical cells are the devices which converts chemical energy into electrical ener
or electrical energy into chemical energy by means of electrochemical redox reactions. These ce
consist of two electrodes immersed in a suitable electrolyte. They are broadly classified as follov
Electrochemical cells
I
Primary cells Secondary cells
Galvanic cell or voltaic cell is a device which converts chemical energy into elect
energy. The free energy change of the redox reaction at the electrodes is transformed into elect
energy. Eg: Daniel cell, Batteries.
Galvanic cells are further classified into two types.
a. Primary Cell (Irreversible): In this, the cell reaction is not reversible. They ar
rechargeable. Eg: Dry cell, Zn- Ag 20 cell and Zn-air battery and Li-Mn0 2 battery.
b. Secondary Cell (reversible): In this, cell reaction is completely reversible and recharg1
Therefore we use over and over again. These are also called as storage cells. Eg: Lead
storage battery. Ni-Cd battery. Ni- Metal hydride battery & lithium ion battery.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
Electrolytic Cell is a device which converts electrical energy into chemical energy.
Eg: Electroplating of metals, electrolysis of water.
Definations
Single electrode potential: Single electrode potential is the potential developed at the interface
between metal and its solution when it is in contact with a solution of its own ions and the two
are in equilibrium with each other. It is denoted by 'E'.
Standard electrode potential: Standard electrode potential is the potentittl developed when
the pure metal electrode is in contact with a solution of its ions of unit concentration at 298 K.
If the electrode involves gas, then the gas is at 1 atmo~pheric pressure. It is denoted by E0 •
Emf of a cell: The potential difference between the two electrodes of a cell which causes the
flow of current from one electrode (high reduction potential) to the other (lower reduction
electrode) is called electromotive force of the cell. It is denoted by Eccll'
Emf of cell = Reduction potential of cathode- Reduction potential of anode
Thus the Net cell reaction Zn + Cu 2+( 1M) -----.• Zn2+ (1M) + Cu
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
Engineering Chemist~
Volt meter
e- ... e- ...
(±)
Salt Bridge
Zn (anode) - - - •
CuSO~ (I M)
ZnS04 OM)
Solution
Solution Porous
plug
Electrochemical conventions
1. There arc two electrodes in galvanic cell. Each of these electrodes is referred to as half cell.
2. If reduction occurs at an electrode, it is called a reduction (positive) electrode or cathode. lf
oxidation occurs at an electrode. it is called an oxidation (negative) electrode or anode.
~
'· :
.>.l
3. The potential of an electrode is always expressed as reduction potential and is represented as
4. The electrode at which oxidation occurs (anode) is written on the LHS and the electrode at
which reduction occurs (cathode) is written on the RHS.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
5. The electrode on the lcfl (anode) is written by writing the metal first and then the electrolytic
solution. For example. ZniZnSO.l
6. The electrode on the right (cathode} is written by writing the electrolytic solution first and then
the metal. For example. CuSO ~!Cu.
7. The single vertical line indicates the phase boundary between the metal and the electrolytic
so!wion and double vertical line indicates the salt bridge
... .
8. The concentration of corresponding electrolytic solutions is represented in the parenthesis.
The arrow mark indicates the directiPn of flow of electrons i.e., from anode to cathode.
For example. a Daniel celi can be represented as:
.. II cu~+ (1M) !Cu
Zn!ZnSO-' ( l M} II CuSO-' (I M) !Cu or Zn!Zn~+ (1M)
Derivation of Ncrnst c<tuation for single electrode potential NOT IN THE SYLLABUS
Ncrnst clcrivccl a thermodynamic equation which relates the change in free energy (~G), electrode
potential <E) and the concentration of metal ions (M +). He considered a reduction reaction or the
11
type.
M(aq) + ne
J.J+
The change in the free energy for spontaneous reaction is related to equilibrium constant (K) by
Van 't Hoff equation:
NOT IN THE SYLLABUS ----- ( l )
L1G = L1G 0 + RT ln K
Where L1G is the free energy change, L1G0 is the std. free energy change
R is the Universal gas constant, Tis the absolute temperature and K is the equilibrium constant.
Equilibrium constant for the reduction reaction of the type, Mn+ + ne- --7 Misgiven by,
For a spontaneous reaction, decrease in the free enngy (- L\G) is the maximum amount or work
and is given by
- L1G = W max ----- fl)
But the maximum amount of work done for an electrochemical reaction depends on the number of
coulombs of electricity that flow and the energy available per coulomb.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
8 Engineering Chemistry
Then, The relationship between free energy change (ilG) and electrode potential (E) is given by
ilG = -nFE ----- (5)
Under standard conditions, NOT IN THE SYLLABUS
ilGu = -nFEu ----- (6)
On substituting (2), (5), (6) in (1 ), we get
Divide equation (7) by -nF, on both sides and converting natural logarithm to the base 10,
We get
2.303RT
E = Eo+ - - - log [Mn+] ----- (9)
nF
On substituting the values for
R = 8.314 1/K/mol
T = 298 K
F = 96500 C/mol, the above equation reduces to
0.0591
E =Eo+--- log [M"+] ----- ( 10)
n NOT IN THE SYLLABUS
The above equation (10) is known as the Nernst equation for single electrode potential.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
Eo 2.303 RT
Ecell = cell+ nF
Ecdl =
. 0.0591 [ Cu 2+]
Ecell = Eo cell +
n
log [
Zn 2
+
J Where ' E0 CC ll -_ E0 Cu 2+ _ E0 Zn2+
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
10 Engineering Chemistry
SOLVED PROBLEMS
Solution :
" 0.0591
E = E + log [M 11 +]
n
(l 0.0591
E = E- log [Cu 2+]
n
l 0.0591
E' = 0.296 - log (0.0 15)
n
E 0 = 0.349V
2. Calculate the voltage generated in the following cell lVln/i\tln 2+ II· Fc2+fFe when
iron rod is immersed in l.OM FeS04 solution and i\tln rod is immersed in O.llVl
1\:fnSO,.. solution. Given E".1- c-'+II'.c =- 0.40 V and E'l\'1n z+1 '', 111 =- 1.18 volt. [Feb, 2001]
Solution :
(i) Cell representation:
Mn!Mn 2+ (0.1 M) II Fc 2+ ( 1.0 M)IFe
( ii) Electrode reactions :
At anode: Mn ~ Mn 2+ + 2e-
At cathode: Fe2+ + 2e- ~ Fe
Net cell reaction: Mn + Fe 2+ ~ Mrl~+ + Fe
E = E'
,.
+_
0.0591 [Fe 2+ J
log -=-[M'------ +::;.]
cdl cdl 2
11 11
0 059 1
E = (E" '+ .. -Eo .,+ ) + - · - - loll _l.O
cdl Fe- /l·c Mn- /Mn 2 ° 0.1
Ecetl = 0.8095 V
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
3. Calculate the potential of Ag-Zn cell at 29HK if the concentration of Ag+ and Zn 2+are
5.2 x w-6 J\1 and 1.3 x 1()·-' l\'1 respectively. E0 of the cell at 298K is 1.56 V. Calculate
the change in free cnerg)' L1G for the reduction of lmole of Ag+. [July, 2006]
Solution :
0
\Ve know from electrochemical series that, E(,); g+ 1"g
, > E • .,
Zn - /Zn
so Zn becomes anode and A2:'-
become cathode.
At anode:
At cathode:
Net cell reaction:
.. Ecell = E0 .. 11 +
0.0591
11Jog
[ Ag+
[ zn-,,
TJ
,, n lY
0.0591
= 1.56 + 2 log '-
~G = -128.62 kJ/mol
4. Calculate the potential of Ag-Cu cell at 298K if the concentration of Ag+ and Cul+ arc
4.2 x l0-1' M and 1.3 x 10·3 J\11 respectively. Given E"Ag + /Ag = 0.80V, E"cu 2+ 1cu = 0.34V of
the cell at 298K. Calculate the change in free energy L1G for the reduction of I mole
of Ag+.
[Jan, 2004]
Solution :
At anode: Cu -7 Cu:!+ + 2c-
At cathode: [Ag++ e- -7 Ag] x 2
12 Engineering Chemistry
2
o 0.0591 (Ag+]
Ecdl = Eccll + lol!..., [ C ,,<.+ ]
n ,u
2
0 0591 [ 4 2 X 10-(, ]
= (0.80-0.34) + · log -:::--·---
2 [ t.3 x 1o-3 J
= 0.46 + 0.02955 log [ 13.56 x tO-'~]
5. The E11 values of Jj+/Li , Zn 2+/Zn, Cu 2+/Cu and Ag+/ Ag are - 3.0V, -0.76V, + 0.34V,
and +0.80 Volts respectively. \Vhich combination of the electrodes you usc to construct
a cell ot' highest emf, if the ionic concentrations nrc O.lM, l.Ol\1, 101\'1 and ().() lM in
the same order. .Justify your answer. [July, 2005]
Solution :
The potential of a half cell is
0.0591
E = 0.34 + log (1 0.0) =0.34 + 0.02955 x 1
2
= 0.3695 v
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
Electrochemistry & Battery Technology 13
0.0591
E = 0.80 + log (0.0 I)
= 0.6818 + 3.0591
Ecell = 3.7409 V
6. Calculate the emf of the cell Fe /Fe 2+(0.011\tf) II Ag+ (O.lM)/Ag at 298K, if SRP of Fe and
Ag are- 0.42 and 0.8V respectively. [VTU, Jan 2008]
~.:
, Solution :
:t~
:~
'~ At anode: Fe ---7 Fe2+ + 2e-
~d
(l 0.0591
Eccll = Eccll + log
11
')
E _ (E -E ) 0.0591 l (0.1r
cell - Ag+/Ag
2
Fc +/Fc + 2 og [0.01]
Solution :
(i) Cell rcpresentalion :
MniMn~+ (().I M) II Fe 2 + ( 1.0 tv{) ! Fe
(ii) Electrode reactions :
At anode: Mn -7 Mn 2+ + 2e-
At cathode: Fe 2+ + 2e- -7 Fe
Net cell reaction:
(iii) The em!' of the cell is :
[Fe _,_ J
2
( 0.0591
E' + - - - loo -="----=
= ccll n c [Mn2+ J
1.0
I Ecdl log-
! ~ 0.1
= [-0.44-(-1.1 X)j + 0.02955 = 0.74 + 0.02955
E cell = 0.7696 V
o 0.0591 [Ag+]
Ecell = Ecell +
n log [ Fe-+
, J
7
II II ) o.o59t [o;osr
Ecell = ( E Ag + /Ag - E Fe-'+ /Fe + 2 tooo [ 0.1 ]
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
E
cell
- Eo + 0.0591 loo [ Ag+
- cell n o [ Cd 2+
JJ
?
16 Engineering Chemistry
[ Pb +]
2
1) Metal-Metal ion electrodes: These are the electrodes where a metal is dipped in a solution
containing its own ions. Eg: CuiCuSO 4, ZniZnSO 4
2) Gas electrodes: These are the electrodes where a gas is in contact with an inert metal like
Pt foil which is dipped in an ionic solution of gas molecules. Eg: Hydrogen electrode.
3) Metal-Metal Insoluble salt electrodes: These are the electrodes where a metal will be in
contact with a insoluble salt of the same metal dipped in a solution containing anions of the
salt.
Eg: Calomel electro.de (HgiHg 2 Cl~lcn, Silver-silver chloride electrode (AgiAgCliCn.
4) Ion selective electrodes: These are the electrodes which are sensitive to particular ionic
species and will develop a potential when a membrane is in contact with an ionic solution. Eg:
Glass membrane electrode
5) Redox electrodes: These are the electrodes, where the inert metal like Pt will be in contact
with oxidized and reduced forms of the same metal in solution. The electrode potential arises
due to the presence of both oxidized and reduced species of the same metal at an inert
electrode like Pt. Eg: Pt/Fe2+;Fe3+, Pt/Cr3+;Cr6+, Pt/Sn~+;Sn4 +
Reference electrodes
Reference electrodes are those electrodes which have constant reduction potential and
which are used to determine the electrode potential of other electrodes. There are two types of
reference electrodes.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
Secondary reference electrodes : These are the type of electrodes whose reduction potential
remains constant and their potential is measured w.r.t SHE and can be used as reference
electrode for measuring potential of other electrodes and for various analytical analysis.
Advantages
1) Calomel electrode is easy to construct and portable
2) Cell potential is reproducible.
3) Potential is stable over a long period.
4) It can be used in the presence of strong oxidizing agent.
Applications
1) It is used as a secondary reference electrode in the measurement of electrode potential of
other electrodes.
2) It is used as reference electrode in all potentiometric titnitions.
3) It is used as reference electrode with· glass membrane electrode in pH determination.
.-----External contact
Saturated KCl
~ Ag (s) +
The overall electrode reaction: AgCl(',lll) + e- ,..,.r=:::=:::.. cr .(<lljJ
20 Engineering Chemjstry
Advantages
1) It is easy to construct and portable.
2) Its superior tempera~ure stability makes it usable even above 130°C.
3) The potential remains constant as long as the chloride concentration remains constant.
4) The potential is stable over a long period.
Applications
1. It is used as an internal reference electrode in glass membrane electrode.
2. It is used in determining the potential distribution on the ship's hulls and oil pipelines.
3. It is used in corrosion studies.
Graphite
he electrode. In case of Zn electrode it takes negative sign and is assigned as anode. Calomel
~lectrode takes positive sign and assigned as cathode.
c) Calculation
on selective electrodes
Ion selective electrodes are tlze electrodes which are sensitive to certain specific ions
resent in the solution and they develop the potential with respect to that species. Eg: Glass
1embrane electrode.
Glass membrane electrode is an ion selective electrode in which a thin membrane present is
ermeable only to H+ ions and not to other ions in the solution. It develops the potential if any
hange in the H+ ion concentration.
22 Engineering Chemistry
,-----External Contact
Test solution
Unknown [H+] =C2
0 Internal Ref. solution
C1 = 0.1 M HCl
Ag/AgCl
~ ~
= 2.303RT I C 2.303RT
Eh nF og 2- nF log C1
Where 0
E G = L + EAg/AgCI + Eassy· E0G is the combination of 3 constant terms.
Advantages
a) Accurate results are obtained between pH range 1 - 9.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
24 Engineering Chemistry
Disadvantages
a) Glass electrode cannot be used in presence of fluoride ions.
b) Glass electrodes are very thin and fragile, should be handled with care.
c) It requires special glass membrane for solutions of pH less than 0.5 and more than 10.
d) Glass membrane has high internal resistance; ordinary potentiometer is not employed and
hence requires vacuum tube voltmeter (VTVM) .This is relatively costlier when compared to
ordinary potentiometers.
Glass membrane
SCE (Anode) electrode (Cathode)
Solution of unknown pH
H _ E~ -ESCE -Ecdl
p - 0.0591
E0G value is calculated by dipping the glass membrane electrode in a solution of known pH
and measuring the emf of the cell when combined with a calomel electrode.
Concentration cells
A concentration cell is a galvanic cell which generates electrical energy at the expense
of chemical energy. In concentration cells, electrode and electrolyte present in both half
cells are same but the concentration of electrode or electrolyte is different. Concentration calls
are classified into two types: ·
1. Electrode concentration cells and 2. Electrolyte concentration cells
Electrode concentration cells: In these cells, the concentration of electrolyte is same.
The two electrodes contain the same material but with different concentrations.
Ex: (1) Two hydrogen electrodes having hydrogen gas at different pressures, dipped in the same
electrolytic solution. It is represented as: Pt/H 2 (P 1)1HCI (x M)/H 2 (P:)!Pt
Where, P, and P2 are the pressure at which H2 gas is maintained at anode and cathode
respectively. P1 > Pr
The half cell reactions are
At Anode: H (P,) _ _ ___. 2H+ + 2e-
2
26 Engineering Chemistry
C, and C2 are concentrations of Zn2+ in the two half cells respectively and C:? C,.
Emf of a concentration cell can be calculated using Nernst Equation as follows:
2.303 RT
0
E annJc = E anotlc + nF
2.303 RT
0
Ecathode = E cathode + nF log C2
2.303 RT 2 303 RT
= [E0cathode + nF loob C2] - [E0anode + · nF log C 1]
2.303RT (C2]
Eccll = nF log [C1]
By substituting the values of R, T and F we get,
SOLVED PROBLEMS
1. A concentration cell was constructed by immersing two silver electrodes in 0.011\1 and
10M AgNO~ solutions. Write the cell reactions and calculate the emf of the concentration
cell. [VTU, July 2005]
An electrode of higher concentration of Ag+ (1OM) acts as cathode, while the other silver
electrode with Ag+ ion concentration (O.OlM) acts as anode.
(i) Cell representation:
Agl Ag+ (0.01 M) II Ag+ (10M) I Ag
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
28 Engineering Chemistry
0.0591 (C2]
Eccii = n log [C,]
0.0591 [10]
E.:cll = 1 log [0.01]
2.303 RT I (C2]
Eccu = nF og (C,]
= 0.02976log 100
= 0.02976 x2
Eccll = 0.05952 V
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
0.0591 (C2]
Eccll = n log (Ct]
0.0591 [1]
Eccll = 1 log [0.05]
= 0.0591log20
= 0.0591 X 1.3010
Ecell = 0.07689 V
4. The emf of the cell Cd/CdSO i0.0093 M) II CdSOix M) /Cd is 0.086V at 25°C. Find
the value of x. [Jan 2010]
0.0591 (C2]
Eccll. = n log (Ct]
0.0591 [x]
0.086 = log [ ]
1 0.0093
[x]
l og [0.0093] = 2.910
30
0.0591 [C2]
Eccll = n log [C1]
l ( x] = 1.252
og [0.0083]
0.0591 [0.064]
n = 0.0126 log [0.024]
REVIEW QUESTIONS
ELECTROCHEMISTRY
2. Define (i) single electrode potential and (ii) standard electrode potential?
(Jan 2013) (Dec 2011)
3. Derive Nernst equation for a single electrode potential? (Jan 2013) (July 2013) (Jan2015)
5. What are reference electrodes? List the limitations of primary reference electrode?
6. What are secondary reference electrodes? Mention the requirements of secondary reference
electrodes?
7. What are the advantages of secondary reference electrodes over primary reference electrodes?
9. What are secondary reference electrodes? Explain the construction, working and applications
of Ag/ AgCl electrode?
10. What are reference electrodes? Explain the determination of electrode potential of an unknown
electrode using calomel electrode? (Jan 2014) (Jan 2015)
12. Explain the construction, working and applications of Glass membrane electrode? (Jan 2011)
13. What are the advantages and limitations of glass membrane electrode?
14. Explain how glass membrane electrode can be used in determination of pH of unknown
solution?
(Jan 2011)
15. What are concentration cells? Give its classification with examples?
16. What are electrolyte concentration cells? Deduce an expression for the EMF of a concentration
cell? (Dec 2011) (Jan 2014)
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
32 Engineering Chemistry
Introduction
A battery is an electrochemical device which produces electricity by means of redox
chemical reactions. It consists of one or more galvanic cells connected in series or parallel
or both. It stores chemical energy in the form of electro active materials and on demand converts
it into electrical energy through redox reactions. Thus, a battery acts as portable source of electrical
energy.
Batteries are widely used as sources of D.C electrical energy in automobiles, boats, aircraft,
ships, portable electric/electronic equipment and lighting equipment. In some instances, they are
used as the only source of power; while in others, they are used as a secondary or standby power
source.
The working principle of a battery is the electrochemical conversion of free energy of redox
reactions of the electrode active materials into electrical energy.
1) The anode [-ve electrode] is oxidised during the electrochemical redox reaction and liberates
electrons to the external circuit.
The materials ~aving the following properties are preferred as anodic material. It should be
an efficient reducing agent; it should have low reduction potential, good conductivity, good
stability in contact with electrolyte, ease of fabrication and low cost. The following metals can
be used as anode: zinc (cheap metal), lead, cadmium and lithium (lightest metal) etc.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
34 Engineering Chemistry -
The secondary battery can act both as galvanic cell and electrolytic cell. During discharging
[fig. 2(a)] it acts as a galvanic cell, converting chemical energy to electrical energy and during
charging [fig. 2(b)] it acts as an electrolytic cell converting electrical energy to chemical energy.
- +
i) Emf of a battery
The voltage of the battery depends on the total number of cells. which constitute a battery.
The overall reaction of a battery is given as,
M I+ Mn+
2
.;:::=~"'"~
.....
Mn+
I
+ M2
Then, the emf of a cell
and Q is the Reaction Quotient for the cell reaction at any stage of the reaction which is
the ratio of the ionic concentrations of M~+ and M~+ :
It is evident from the above relation that, the emf of a battery dependents on.
(i) Eocell (Difference in the standard reduction potential between the cathode and anode). Higher
the difference higher is the emf of a battery.
(ii) Emf of the battery decreases with increase in the ratio of the ionic concentration of M~+ and
M~+ and
(iii) With increase in temperature emf of a battery decreases marginally.
ii) Current
It is the· rate of discharge reactions of the cell and is measured in amperes. One ampere
of current is said to flow when one coulomb of electrons pass through a point in one second. It
depends on the amount of active materials. Higher the amount of active materials stored emf is
generated for longer time.
iii) Capacity
The capacity of~ battery is expressed as the total quantity of electricity that can be
obtained from the battery. lt_is expressed in ampere-hours (A-h) or Watt-hours (W -h)
The total number of ampere-hour or watt-hours that can be withdrawn from a fully charged
battery under specified conditions of discharge is termed as the capacity of a battery.
The theoretical capacity of a battery is the quantity of electricity involved in the electro-
chemical reaction. It is denoted by C and is given by:
WnF
C=M
Where, W = Weight of active material, n = number of electrons transferred per mole of
reaction, F =Faraday's constant and M =Molar mass of the active materiaL The ability of the cell
to continue to ddiver the expected capacity at increased discharge rates is an important battery
property.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
36 Engineering Chemistry
The variation of voltage v/s time during discharge of battery is given below.
LL
~
w
Time
The length of horizontal portion of the curve is the direct measure of the capacity of battery.
Higher the length of the horizontal portion better is the capacity of the battery.
Eg. A battery rated at 100 Ah will deliver 5 A over 20 hours period at room temperature.
However, if it is discharged at 50 A, it will come only for 2 hours that means it will have a lower
apparent capacity.
iv) Electricity storage density
This is a measure of the total current which can be withdrawn from the unit weight of
a substance when it widergoes an electrochemical redox reaction. In other words it is the
capacity per unit weight i.e. electricity storage density is the amount of electricity per unit weight
which the battery can hold.
Eg. 7g of lithium is required at anode to give 96500 Coulombs whereas for the same charge,
65g of zinc is required. To get high storage density the mass of subsidiary elements should be
mmtmum.
v) Energy efficiency
It is applicable to a rechargeable battery. Energy efficiency for the storage batteries is given
by
energy released on discharge x 100
% energy efficiency =
energy required for charge
Construction
.. ·..... ..
.........
. ..
.........
. ·.. ·.. · .· .·· .· .· .· .·
......
. .· .· .· .· .· .· . .· . .. ·. .· .·.· ....
.
.. .. .. ... ..· .......... .
• • 0 • • • • • • • • • •
Cathode end
38 Engineering Chemistry
Anode - granulated Zn powder mixed with aqueous electrolyte and gelling agent.
Cathode - Carbon!catalyst (MnO) mixture coated on nickel plated steel mesh.
Electrolyte- KOH 6M
Seperator - Polypropylene (PP)
It is represented as : Zn/6M KOH/ Air/C
--•~zno
Advantages
1) Light weight and provide high energy density.
2) Flat discharge voltage of 1.3 V.
3) Long shelf life (sealed)
4) Eco-friendly
5) Low cost
6) Capacity independent on load and temperature.
Applications
Zn-air batteries have been successfully employed as a power source for hearing aids. Other
applications include electronic pagers, voice transmitters, portable battery chargers, military radio
receivers, rail road signaling, medical devices and so on.
2. Nickel - Metal hydride battery
A relatively new technology is adopted in the case of the chargeable nickel - metal hydride
battery with characteristics similar to those of the Ni-Cd batteries. The Ni ~M~ battery uses
hydrogen absorbing metal alloy (M~) as the active negative material whereas cadmium is used in
the Ni-Cd battery and that makes the noticeable difference between the two.
Smaller amount of the negative electrode is sufficient in the Ni-metal hydride battery. Hence
higher energy density can be achieved in the case of metal hydride battery than the Ni-Cdbattery.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
This allows for a larger volume for the +ve electrode, which results in a higher capacity of the Ni-
metal hydride battery. Moreover, the metal hydride battery is free from Cd, hence it is environmentally
friendly than the Ni-Cd battery and may reduce the problems associated with the disposal and
recycling of batteries.
Construction
Cell cap
Contact spring
Sealing washer
Anode
Seperator - - - - - - .
Cathode -------...1
40 Engineering Chemistry
The discharge electrode reactions of the Ni- MH2 battery are as follows:
At anode
At cathode
2Ni0(0H) + 2H20 + 2e- _......,.. 2Ni(OH) 2 + 20H-
The overall reaction during discharge is,
discharging
MH2 + 2Ni0(0H) ,.. M + 2Ni(OH) 2
The process is reversed during charge
charging
M + 2Ni(OH\ ,.. MH2 + 2Ni0(0H)
The net cell reaction during discharging and charging can be represented as
As can be seen from the overall reaction above, that the hydrogen moves from the +veto -ve
electrode during charge and reverses during the discharge. The electrolyte does not directly take
part in the overall reaction, which means that there is no decrease or increase in electrolyte
concentration. It produces an emf of 1.35 volts.
Advantages
1) High capacity (30- 40 %) compare to Ni-Cd battery.
2) Environmentally friendly- contains only mild toxins; profitable for recycling.
3) Rapid recharging capability
4) Long cycle life and shelf life in charged state
5) Less prone to memory effect than the Ni-Cd battery
6) Simple storage and transportation
Limitations·
1) Performance degrades if stored at elevated temperatures.
2) Battery requires regular full discharge to prevent crystal formation.
3) About 20 % more expensive than Ni-Cd battery.
Applications
The nickel-metal hydride batteries are 1.1Sed in lap top computers, cellular phones and camcorders.
It is also used in electrically driven vehicles. It has high potential for 2 and 3 wheelers in Asian
countries.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
3. Lithium Batteries
Introduction
Lithium metal is the excellent choice as anode material because of light weight (0.534 g/cm 3
at 2SO C), has low reduction potential (-3.0V) and provides the largest specific energy per weight.
Lithium batteries are available as primary and secondary batteries. In primary batteries Li metal is
used as anode electrode. But in rechargeable batteries because of the inherent instability of lithium
metal, especially during charging it is not used as an anode electrode but a carbon matrix material
is used instead of it as the negative electrode which during charging, takes up lithium ions by
cathodic intercalation.
Pioneer work with the lithium battery began in 1912 under G.N. Lewis, but it was not until the
early 1970s that the first non-rechargeable lithium batteries became commercially available. Attempts
to develop rechargeable lithium batteries started in the 1980s.
(i) Lithium-Manganese dioxide (Li-Mn0 2) primary battery
The most commercially used modern primary battery is the lithium-manganese dioxide solid
cathode battery. It is available in many configurations [coin, bobbin, prismatic] and is designed for
low, moderate and high capacity applications.
Construction
Anode Can
Cathode Separator
+
Electrolyte
Figure 5. Litlzium-Mn02 primary battery
The schematic representation of lithium primary battery is shown in figure 5. It uses lithium as
the anode and heat treated manganese dioxide as the cathode active material and an electrolyte
containing lithium salts mixed in organic solvent [propylene carbonate and 1, 2 dimethoxy-ethane J.
Anode Lithium metal
Cathode heat treated Mn0 2
Electrolyte Lithium salts like LiCl, LiBr mixed in organic solvents like propylene carbonate
and 1, 2 dimethoxy- ethane
Separator Non woven PP immersed in the electrolyte
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
42 Engineering Chemistry
At cathode,
Advantages
1) High volumetric and gravimetric energy density due to low weight ofLi.
2) Wide operating temperature range [-40 to 70°C],
3) Performance at high discharge rates,
4) Superior shelf life,
5) Relatively low cost.
Applications
The lithium-manganese cell is used in a wide variety of application such as long term memory
back up, safety and security devices, lighting equipments and many consumer electronic devices
such as watches, calculators etc.
(ii) Lithium-ion rechargeable batteries NOT IN THE SYLLABUS
It was thought that rechargeable batteries with lithium metal as the anode (negative electrodes)
could provide extraordinarily high energy densities; however, it was discovered in the mid 1980s
that discharging and charging produced unwanted dendrites on the anode. These dendrite particles
penetrate the separator and cause an electrical short. Due to this, the cell temperature rises quickly
and approaches the melting point of lithium, causing thermal runaway, also known as "venting with
flame." [Also the poor reversibility of the lithium electrode. During hattery charging, spongy lithium
is deposited from the solution. This deposit rapidly loses contact with the bulk of the lithium electrode.
(due to rapid oxidation) Hence, with every discharge-charge cycle of a battery, the amount of
lithium participating in the electrode reaction decreases and the battery's discharge cag(lcity drops
off.]
The design of lithium ion batteries has been a great achievement toward overcoming this
defect. In 1991, Sony commercialized the first Li- ion battery, and today this battery has become the
most promising and fastest growing on the market.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
Construction
The schematic representation of lithium ion rechargeable battery is shown in figure. 6. The
carbon matrix material (graphite) is used as the negative electrode (anode) which during charging,
takes up lithium ions from cathodic electrode. Materials for the positive electrode (cathode) are
selected among those which, unlike carbon, will intercalate lithium ions during discharge while
retaining a sufficiently highly positive value of potential. During charging of these electrodes, lithium
ions undergo deintercalation. Common cathode materials are Lithium Cobalt Oxide (or Lithium
:obaltate, LirCo0 2), Lithium Manganese Oxide (or Lithium Manganate, LirMn 20), Lithium
·1ickel oxide (LirNi02), Lithium Iron Phosphate (LiFeP04). The electrolyte is typically a combination
)f lithium salts·, such as LiPF6 , LiBF4, or LiC104, in an organic solvent, such as ether.
Discharge Load or
Cu-foil
discharge
Cell reaction, - - - - . . 6C + LiCo0 2
Engineering Chemistry
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
During discharge, lithium ions spontaneously move from the anode (graphite) to cathode
(LiCo0 2) and the e- flow through the external circuit.
charge
During charging~ 6C + LiCo0 2 • LiC 6 + Li 05Co0 2
During charging an external power supply forces thee- to flow through the external circuit
and allows lithium ions to travel from LiCo0 2 electrode to graphite electrode.
The net cell reaction during discharge and charging can be given as
·c _ . C discharging
L1 6 + L105 o0 2 ----• 6C + LiCoO..,
NOT IN THE SYLLABUS
~
chargmg
.
In summary, during discharge, the lithium ions t1ow from the anode to the cathode through the
electrolyte and separator~ charge reverses the direction and the Li ions flow from the cathode to
the anode. For this reason the term rocking-chair batteries was coined for batteries of this type.
Figure 7 illustrates the process.
NOT IN THE SYLLABUS
\ \
Anode
\
I
Cathode (Li
(Carbon)
Metal Oxide)
\dvantages
1) Lighter than other rechargeable batteries for a given capacity \
2) Li-ion chemistry delivers a high open-circuit voltage
~) Low self-discharge rate (about 1.5% per month) NOT IN THE SYLLABUS
n Do not suffer from battery memory effect
i) Environmental benefits: rechargeable and reduced toxic landfill.
i) Low maintenance - no periodic discharge is needed.
') Long cycle life.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
Limitations
I) Safety concerns if overheated or overcharged NOT IN THE SYLLABUS
2) Poor cycle life, particularly in high current applications
3) Rising internal resistance with cycling and age
4) Shipment of larger quantities of Li-ion batteries may be subject to regulatory controL
5) About 40 % higher in cost compare to Ni-Cd battery.
Applications
1) For portable applications such as laptop, cellular telephones, video cameras, digital cameras,
DVD players, MP3 players, portable games machines etc.
2) Medical applications include emergency lighting, defibrillator machines and pacemaker devices.
3) In heavy industry, including electric power trains for vehicles
4) All forms of sustainable energy, such as wind turbines or photovoltaics, require excellent
energy storage systems. The lithium ion batteries are the potential of energy storage systems
compared to other carbon anode based batteries.
Fuel cells are electrochemical devices in which chemical energy of a fuel is directly
converted into electrical energy by means of redox reactions involving fuels and oxidants.
Fuel cell does not store energy but converts the chemical energy available in the fuels into electrical
energy directly.
Fuel cell also has two electrodes and an electrolyte. The fuel and the oxidant are continuously
and separately fed into anode and cathode electrodes respectively, at which they undergo oxidation
and reduction generating electrical energy.
Fuel cell may be generally represented as
Load
e e
A(-) C(+)
At Anode
CH~OH + H20
At Cathode
(Yz 0 2 + 2H· + 2e- --~Jio H20) x 3
Advantages
(i) Like hydrogen, methanol does not have storage problems.
(ii) It has higher energy density than H2 , though lesser than gasoline or diesel.
(iii) Easy to transport and supply to the customer.
Applications
Methanol-oxygen fuel cell is used in wireless head sets for mobile phones [8.5 gram weight],
in laptops, military applications and in large scale power production.
UNIT-2-ELECTROCHEMICAL ENERGY SYSTEMS
Electrochemistry & Battery Technology 49
REVIEW QUESTIONS
BATTERY TECHNOLOGY
11+11+11 + 11+11+11