Chapter 2

Electrochemical energy systems

 Overview of syllabus
Unit II: Electrochemical energy system (8 hours)
Faradays laws, origin of potential, electrochemical
series, reference electrodes, Nernst equation,
introduction to batteries – classification – primary,
secondary and reserve (thermal) batteries.
Characteristics – cell potential, current, capacity and
storage density, energy efficiency. Construction, working
and application of Leclanche cell-Duracell, Li-MnO 2 cell,
lead acid batteries. Ni-Cd battery, Lithium ion batteries.
Fuel cell - construction and working of PEMFC.
 Common terminologies
• Potential :The potential is the basic expression
of electrical energy. By potential, what we
mean is potential difference and it is
commonly known as electromotive force.
Unit - Volts
• Current (I): Intensity of current flowing.
Unit - Ampere
• Electric charge (Q): Amount of current in a
given time = current x time. Unit - Coulomb
 Faraday’s laws of electrolysis
• First law: During electrolysis, the amount of
chemical reaction which occurs at any electrode
under the influence of electrical energy is
proportional to the quantity of electricity
passed through the electrolyte.
W ∝ Q
W ∝ It
W = ZIt
Z = Electrochemical equivalence
 W = ZxIxt
When 1 Amp of current is passed for 1 sec
(1coulomb)
W =Z
‘Z’ is the mass of substance that is deposited or
altered when 1 Amp of current is passed for 1
sec (1coulomb)
• Second law: states that for a given quantity of
electricity, the mass of substance altered at
electrodes of different cells connected in
series will be directly proportional to their
equivalent weights.
@Anode – Cl2 ↑ @Anode – HNO3
+ O2 ↑
@ Cathode –
NaOH + H2↑ @ Cathode–Ag↓

NaCl AgNO3

If current is passed long enough to deposit 35.5 g of Cl 2 by the same time

40 g of NaOH
1 g of H2
8 g of O2
63 g of HNO3
108 g of Ag……..
Also would be formed
• The quantity of electricity needed to deposit
I equivalent weight of any substance =
1 Faraday = 96500 C

1 F = Charge of one mole of ens

= 1.632 x 10-19 x 6.023 x 1023
= 96500 C

Remember
From 1st law: W = Z Q
E = Z x 96500 C
Z =E/F

From 2nd law: W1 / W2 = E1 / E2

 Problems
Q1 : 0.1978 g of Cu is deposited by a current of
0.2 A when passed for 50 minutes. Calculate
the electrochemical equivalence of Cu.

W=ZIt
0.1978 = Z x 0.2 x 50 x60
Z = 0.1978/0.2x3000
Z = 0.000329 g
Q2. What current strength in amperes is needed
to liberate 10 g of iodine from KI solution in 1
hour? Give Eq. Wt. of I2 = 127 g

w=ZxIxt
Z = E/F = 127 /96500

10 = 127/96500 x I x 60x60
I = 2.1 A
Q3. An electric current is passed through 3 cells connected in series
containing CuSO4, AgNO3 and KI solutions. What weights of Ag and
I2 will be liberated by the time 1.2 g of Cu is being deposited? Given
that Eq. Wt. are 32g, 108g and 127g for Cu, Ag and I2 respectively

For Cu and Ag For Cu and I2

WCu / WAg = ECu / EAg WCu / WI2 = ECu / EI2

1.2/ WAg = 32/108

1.2/ WI2 = 32/127

WAg = 4.05 g
WI2 = 4.76 g
Origin of electrode potential

Zn  Zn+2 + 2en

When a metal rod is kept immersed in its salt solution,

some metal atoms go into solution as ions, leaving behind
the electrons in the metal lattice. For example when a zinc
rod is kept immersed in zinc sulphate solution, zinc goes
into solution as zinc ions. The electrons in the metal
lattice and the positive ions in the solution orient
themselves in an array called electrical double layer, as
shown in figure
 At this stage some of the metal ions return to metal
lattice, by combining with electrons. Soon,
equilibrium is established between the metal atoms
and the ions, which is dynamic. At this stage a
potential is generated at the Zn rod.
Zn  Zn    2e 
The zinc rod is now called zinc electrode.

The formation of electrical double layer and the onset of equilibrium

are responsible for the generation of potential. This equilibrium
potential is called single electrode potential. A direct way to establish
this fact is to measure the potential. But as described earlier, the
potential is the potential difference. For this, another such system is
needed. A copper metal in contact with its ions may be taken as the
other electrode. Formation of double layer and establishment of
equilibrium between copper and its ions occur in the system.
Cu  Cu    2e 
 The Zn and Cu are externally
connected by a conducting
wire, which provided a path
for the flow of electrons. The
two electrolytes are
connected by a salt bridge,
which facilitates ionic charge
transfer

A voltmeter, if connected across the two electrodes (zinc and copper), will
record a potential difference. This is a direct proof for the generation of
potential at the two electrodes. This system is an electrochemical cell and
each electrode is a single electrode or a half cell. The potential difference
arises from chemical reactions that occur at the electrodes. In an
electrochemical system the basic reactions are simultaneous oxidation
and reduction
• The next aspect is to find out the sites of oxidation and reduction in the
cell.
• Zinc is more electropositive or baser than copper and hence has a higher
tendency to undergo oxidation. Copper is nobler or more electronegative
than zinc and hence has a higher tendency to undergo reduction. When
the two are combined in the cell, zinc undergoes oxidation
spontaneously. The equilibrium is disturbed and shifted to right.
Zn  Zn+2 + 2en
The electrons travel through zinc lattice, pass through the metallic wire
and reach copper electrode. There they combine with copper ions from
the solution to form metallic copper, which deposits on the copper rod.
The equilibrium is shifted to the left i.e., copper ions are reduced.
Cu  Cu+2 + 2en
The overall cell reaction is oxidation of zinc and reduction of copper ions.
Physically the overall reaction is dissolution of zinc and deposition of
copper. This electrochemical system is called a ‘Redox’ system, since
reduction and oxidation occur simultaneously.
• @ Anode  oxidation ens released
• @ Cathode  reduction  ens accepted

Zn  Zn+2 + 2en
Cu +2
+ 2en  Cu
_______________________
Net reaction Zn + Cu+2  Zn+2 +Cu

Cell notation Zn/Zn+2 (M)//Cu+2(M)/Cu

• Likewise, any two metals can be combined, and a cell
can be constructed. One of them will undergo
oxidation and the other reduction. Hence the driving
force for the occurrence of chemical reaction in an
electrochemical cell is the difference in the oxidizing or
reducing tendency of the two electrodes. The oxidizing
tendency of a metal electrode is called its oxidation
potential and the reducing tendency, the reduction
potential. For assigning numerical values to the
oxidation or reduction potentials, hydrogen electrode
is chosen as the reference.
 Conditions:
1. H+ concentration is 1 M
2. Temperature 25oC or 298 K.
3. Pressure of hydrogen gas 1
atm.
4. The surface of platinum
should be pure and fresh.

Under these standard conditions

the potential of SHE is arbitrarily
fixed to be zero.

The potential of any other electrode can be determined by coupling it with

SHE and forming an electrochemical cell.
 Electrochemical series
• According to IUPAC convention, the potentials of electrodes under standard
condition are expressed as reduction potential and arranged in the
increasing order. This list is called electrochemical series or EMF series or
standard electrode potentials or equilibrium electrode potentials.
Eqbm Eo Eqbm Eo
Li+/Li –3.01 Pb++/Pb –0.126
K+/K –2.92 H+/H 0.0
Mg++/Mg –2.38 Cu++/Cu+ 0.15
Zn++/Zn –0.763 Hg22+/Hg 0.798
Fe++/Fe –0.44 Ag+/Ag 0.799
Fe++/Fe –0.44 Pt++/Pt 1.2
Ni++/Ni –0.257 Au3+/Au+ 1.4
Sn++/Sn –0.14
 Significance of ECS
• The sign of the potential indicates the spontaneity of the reaction. If it is positive the reaction
occurs from left to right spontaneously i.e., reduction is favoured. If it is negative, oxidation is
spontaneous.
Mn+ + en <==> M
• When the potential of Mg electrode is compared with that of SHE, it is less reducing or more
oxidizing to the extent of 2.38 volts. If the two are coupled in a cell, Mg will undergo oxidation
and hydrogen ion reduction.

• If SHE is combined with copper electrode which is more reducing, the spontaneous cell
reaction is oxidation in SHE and reduction in copper electrode.

• When any two electrodes are combined in this series, one with a lower reduction potential
(higher oxidation potential) undergoes oxidation and the other with a higher reduction
potential, undergoes reduction.

• One with a higher oxidation potential displaces the one lower in the series, with less oxidation
potential. Iron dipped in copper sulphate solution, displaces copper from the solution.

• When the potential difference between two electrodes is large, the oxidation and reduction
occur readily.
 Reversible and Irreversible cells

• A reversible cell is one in which the spontaneous cell reaction can

exactly be reversed when a higher potential than the cell potential is
applied externally to the cell, opposing the cell EMF.

Zn + Cu+2  Zn+2 + CU

When an external potential is applied to the cell opposing the cell

voltage, copper gets oxidized i.e., goes into solution as Cu ++ and zinc
ions are reduced i.e., zinc gets deposited as zinc metal.

Zn+2 + CU Zn + Cu+2

The reactions are exactly reversed and this is a reversible cell.

Irreversible cell: This is one in which the spontaneous reactions
are not exactly reversed, when an external voltage is applied to
the cell.

For example, a pair of zinc and copper electrode are kept

immersed in dilute sulphuric acid

and

are connected
Zn  Zn  2e
2 H   2e   H 2 (Cu )

When an external potential higher than the cell potential

is applied in an opposing way;
Cu  Cu    2e 
2 H   2e   H 2 ( zinc )

Reactions are not exactly reversed

 Reference Electrode

There are some problems faced with standard

hydrogen electrode.
• Setting up of SHE is very cumbersome and
tedious.
• Platinum electrode is highly prone to get
poisoned by traces of impurities in hydrogen
gas. Hence hydrogen gas passed must be in a
high state of purity.
• Reproducibility is of less.
 Calomel electrode
• Calomel is Hg2Cl2 - mercurous
chloride

• Ecalomel = E0calomel – 0.059 log [Cl-]

Hg 2Cl 2 ( s )  2e   2 Hg  2Cl 

Calomel electrode is a type of half cell in which the electrode is mercury

coated with calomel (Hg2Cl2) and the electrolyte is a solution of potassium
chloride and saturated calomel.
Saturated Calomel electrode (SCE)
Advantages Disadvantages

Compact and easy to Interference from K+ and Cl-

transport ions
Easy to set up & maintain Can’t be used above 500C
( Calomel decomposes)

Reproducible potentials Toxicity of mercury

Potential does not vary Potential may vary with

much with time and concentration of KCl
temperature
Ag - AgCl electrode
Composed of a silver wire,
coated with a layer of solid
silver chloride, immersed in
a sat. solution of KCl and
AgCl.

AgCl(s) <=> Ag+ + Cl-

E0 = +0.222 V

Advantages
Simple construction
Inexpensive to manufacture
Stable potential
Non-toxic components
 Nernst Equation
• Variation of potential with concentration
• From thermodynamics

ΔG = ΔGo + RT ln k

Dividing it by – nF
RT
-ΔG/nF = -Δgo/nF – nF
ln k ( ΔG = -nFE)
0.0592
E = Eo -n log K (substituting R, T, F and converting to natural log)

Consider an electrode

Mn+ + ne– → M K = Product/Reactant = [M]/[M]n+

0.0592
E = Eo - n
log [M]/[M]n+

E = Eo - 0.0592 log 1/[M]n+ (The activity of the metal is unity)

n
This is Nernst equation for an electrode
• Nernst equation for a cell
Zn + Cu2+ ⇌Zn2+ + Cu
E = Eo - (0.0592/n) log K
E = Eo - (0.0592/n) log [Zn2+] / [Cu2+]
E = Eo - (0.0592/n) log [products] / [Reactants]

• Nernst equation for SHE

2H++ 2e → H2
E = Eo - (0.0592/n) log [products] / [Reactants]
E = Eo - (0.0592/n) log [H2]/ [H+]2 But [H2] = 1
E = Eo + (0.0592/n) log [H+]2
E = (0.0592/2) log [H+]2 (For SHE, Eo = 0, n=2)
E = 0.0592 log [H+]
E= - 0.0592 pH
 Problems
Q1. The standard electrode potential of zinc
ions is 0.76V. What will be the potential of a
2M solution at 300K?

E = Eo – [(2.303RT)/nF] × log 1/[Mn+]

= 0.76 – [(2.303×8.314×300)/(2×96500)] × log ½
= 0.76 – [0.0298 × (-0.301)]
= 0.76 + 0.009 = 0.769V
Q2. What is the Cell Potential of the
electrochemical cell in Which the cell
reaction is: Pb2+ + Cd → Pb + Cd2+ ; Given that
Eocell = 0.277 volts, temperature = 25oC, [Cd2+]
= 0.02M, and [Pb2+] = 0.2M.

Pb2+ + Cd → Pb + Cd2+
E = Eo - (0.0592/n) log [products] / [Reactants]
= 0.277 – (0.0592/2) × log10(0.02/0.2)
= 0.277 – (0.0296)(-1) = 0.3066 Volts
Q3. The Cu2+ ion concentration in a copper-silver electrochemical
cell is 0.1M. If Eo(Ag+/Ag) = 0.8V, Eo(Cu2+/Cu) = 0.34V, and Cell
potential (at 25oC) = 0.422V, find the silver ion concentration.

Cu  Cu+2 + 2en; 2Ag+ + 2en  2Ag

Net rexn: Cu + 2Ag+  Cu+2 + 2Ag

E = Eo - (0.0592/n) log [products] / [Reactants]

Ecell = E0cell – (0.0592/2) × log(0.1/[Ag+]2)

Eocell = Eocathode – Eoanode = 0.8V – 0.34V = 0.46V

0.422V = 0.46 – 0.0296 × (-1 – 2log[Ag+])
[Ag+] = antilog(-1.141) = 0.0722 M
 Classification of batteries
1. Primary batteries - Batteries that cannot be
recharged once depleted. Primary batteries are made
of electrochemical cells whose electrochemical
reaction cannot be reversed.
Ex: Dry cells, Mercury cells

2. Secondary batteries: are those can be electrically

recharged after use to their original pre-discharge
condition, by passing current through the circuit in the
opposite direction to the current during discharge.
Ex: Lead storage, Lithium-ion, Nickel Cadmium
3. Reserve or thermal batteries: In this, one of the
components of the cell like the electrolyte is separated
from the remaining components, until just prior to
activation. This battery structure is commonly observed in
thermal batteries, whereby the electrolyte remains
inactive in a solid state until the melting point of the
electrolyte is reached, allowing for ionic conduction, thus
activating the battery.
Reserve batteries effectively eliminate the possibility of self-
discharge and minimize chemical deterioration. Most
reserve batteries are used only once and then discarded.
Reserve batteries are used in timing, temperature and
pressure sensitive detonation devices in missiles,
torpedoes, and other weapon systems.
 Battery variants
1. Leclanche Cell – Dry cell
A dry cell is an electrochemical cell consisting of low moisture
immobilized electrolytes in the form of a paste, which restricts
it from flowing. Due to this, it is easily transportable.
Generally, the metal container will be
zinc whose base acts as a negative
electrode (anode) and a carbon road
acts as a positive electrode (cathode). It
is surrounded by manganese dioxide
and low moisture electrolyte like
ammonium chloride paste, which will
produce a maximum of 1.5V of voltage,
and they are not reversible.
Cathode reaxn:
2NH4+ + 2MnO2 +2e →Mn2O3 + 2NH3 +
H 2O

Zinc-Carbon Dry cell Anode reaxn:

Zn → Zn2+ + 2e-
 2. Li-MnO2 cell
They have a metallic lithium anode (the lightest of all the metals) and a solid manganese
dioxide cathode, immersed in a non-corrosive, non-toxic organic electrolyte. They deliver
a voltage of 3.0 V and are cylindrical, button and polymer in shape.

MnO2+Li++e- → MnO2Li
Li → Li++e-
Net Rexn:MnO2+Li → MnO2Li

Low self discharge (< 1 % per year at RT)

Superior shelf life and operational life
Wide temperature range (-20 up to 60oC)
0% lead, 0% mercury and 0% cadmium
Worldwide product support
Safe & reliable
3. Lead-Acid battery

It is a secondary battery. The chemical reactions that occur in

secondary cells are reversible. The reactants that generate an
electric current in these batteries (via chemical reactions) can be
regenerated by passing current through the battery (recharging).

Although lead acid batteries have a low energy density, only moderate
efficiency and high maintenance requirements, they also have a
long lifetime and low costs compared to other battery types.

• Lead peroxide (PbO2) – Positive active material.

• Sponge lead – Negative active material.
• Dilute H2SO4 – Electrolyte.
 Reactions during Discharging:
@anode Pb  Pb+2 + 2e
Pb+2 + SO4-2 PbSO4
-------------------------------------------------------

Pb + SO4-2  PbSO4 + 2e

@cathode PbO2 + 4H++2e  Pb+2 + 2H2O

Pb+2 + SO4-2 PbSO4
--------------------------------------------------------------------------------

PbO2 + 4H+ +SO42- + 2e  PbSO4 + 2H2O

Net reaxn => Pb+ PbO2 + 4H+ + 2SO42- + 2e  2PbSO4 + 2H2O

Reactions during Charging:

@anode PbSO4 + 2e  Pb + SO42-

@cathode PbSO4 + 2H2O  PbO2 +SO42-+ 4H+ + 2e

-------------------------------------------------------

Net Reaxn => 2PbSO4 + 2H2O  Pb + PbO2 + 4H+ + 2SO42- + 2e

https://www.youtube.com/watch?v=HHgPBMMZ26w
Pb-Acid battery (Discharging)
Pb-Acid battery (Charging)
4.
 5. Lithium Ion battery
• https://www.youtube.com/watch?v=VxMM4g
2Sk8U

• https://www.energy.gov/eere/articles/how-do
es-lithium-ion-battery-work
• The positive electrode is lithium-cobalt oxide (LiCoO 2)
• The negative electrode is generally made from carbon
(graphite)
• When the battery is charging up, the lithium-cobalt oxide,
positive electrode gives up some of its lithium ions, which
move through the electrolyte to the negative, graphite
electrode and remain there. The battery takes in and stores
energy during this process. When the battery is discharging,
the lithium ions move back across the electrolyte to the
positive electrode, producing the energy that powers the
battery. In both cases, electrons flow in the opposite direction
to the ions around the outer circuit. Electrons do not flow
through the electrolyte: it's effectively an insulating barrier, so
far as electrons are concerned.
 Advantages of lithium-ion batteries
• More reliable than older technologies such as nickel-
cadmium
• Don't suffer from a problem known as the "memory
effect" (where nicad batteries appear to become harder
to charge unless they're discharged fully first).
• Since lithium-ion batteries don't contain cadmium (a
toxic, heavy metal), they are better for the environment
• Compared to heavy-duty rechargeable batteries (such
as the lead-acid ones used to start cars), lithium-ion
batteries are relatively light for the amount of energy
they store.
 Disadvantages lithium-ion batteries
• The biggest issue is safety: Li-ion batteries will catch fire
if they're overcharged or if an internal malfunction
causes a short circuit.
• Require protection from overcharge & fully
discharge.
• Shows ageing.
• Transportation by air is sometimes difficult.
• 40% more costly than Ni-Cd batteries.
• No established system for recycling large
lithium-ion batteries.
 Fuel cells
• A Fuel Cell is an electrochemical device that
combines hydrogen and oxygen to produce
electricity, with water and heat as its by-product.
• The conversion of the fuel to energy takes place
via an electrochemical process, not combustion
• It is a clean, quiet and highly efficient process-
two to three times more efficient than fuel
burning.
 Fuel cells Vs Batteries
• It operates similarly to a battery, but it does
not run down nor does it require recharging.
As long as fuel is supplied, a Fuel Cell will
produce both energy and heat
• The biggest difference between the two is that
a battery stores energy, while a fuel
cell generates energy by converting
available fuel
 Major applications of Fuel cells
• Transportation - All major automakers are working to
commercialize the fuel cell cars

• Stationary Power Stations- provide supplemental power

and backup assurance (Hospitals)

• Telecommunications- 100% reliable to computers, the

Internet and sophisticated communication networks
• Micro Power- Consumer electronics products like mobile phones,
laptops could gain drastically longer battery power with Fuel Cell
technology
• Military – No Heat and noise
Major challenges of FC technology
• Onboard Hydrogen Storage - Difficult
• Fuel Cell Durability and Reliability – extreme
weathers
• Vehicle Cost
• Safety – risks of H2
• Public acceptance
 Working of Fuel cells

• The process begins when Hydrogen molecules enter the anode

• The catalyst coating separates hydrogen’s negatively charged
electrons from the positively charged protons
• The electrolyte allows the protons to pass through to the cathode,
but not the electrons
• Instead the electrons are directed through an external circuit
which creates electrical current.
• While the electrons pass through the external circuit, oxygen
molecules pass through the cathode
• There the oxygen and the protons combine with the electrons
after they have passed through the external circuit
• When the oxygen and the protons combine with the electrons it
produces water and heat
 PEMFC
Proton Exchange
Membrane Fuel Cells
– This is the leading cell type for
passenger car application
– Uses a polymer membrane as the
electrolyte (Nafion)
– Operates at a relatively low
temperature, below 100oC
– Has a high power density, can vary its
output quickly and is suited for
applications where quick startup is
required making it popular for
automobiles
– Sensitive to fuel impurities
 Adv and Disadv of PEMFC
Advantages Disadvantages
High energy density Needed pure hydrogen

Compact design, Easy and

safe handling Low durability

Fast start-up time Water flooding

Low operating temperature Expensive
Min maintenance Platinum catalyst poisoning
(no moving parts) (CO)
End of Chapter 2