II

Natural Sciences Tripos Part II

MATERIALS SCIENCE
C2 : Electrochemistry

Name............................. College..........................
Dr R. V. Kumar
Michaelmas Term 2014-15
2014 15

C2 - ELECTROCHEMISTRY
Dr R.V. KUMAR
COURSE CONTENT (6 Lectures + 1 Examples Class)

Electrolytes
Aqueous solutions; Molten salts; Ionic liquids; Solid electrolytes
Electrochemical Reactions
Electrode potentials & Nernst equation; Reference electrodes; Concentration
cells; Redox potentials; Kinetics of electrode reactions
Applications
Chemical sensors; Batteries; Fuel Cells; Electrolysis; Photocatalytic redox
reactions
Examples Class (one) / Question Sheet (one)
Resources:
Chemical Metallurgy, JJ Moore, Butterworth-Heinmann (PG14)
Modern Batteries, C Vincent and B Scrosati, Butterworth-Heinmann (Pn118)
Fuel Cell Systems Explained, J Larmire and A Dick, John-Wiley & Sons Ltd (Pn123)
DoITPoMS Teaching & Learning Packages
http://www.msm.cam.ac.uk/doitpoms/tlplib/index.php
The Nernst equation & Pourbaix diagrams
Ellingham diagrams
Kinetics of aqueous corrosion
Batteries
Fuel cells

Introduction
A basic electrochemical cell comprises two electrodes and one electrolyte.
Reactions in electrochemical cells occur when electrons are transferred from one species
to another and are known as redox reactions.
Any given redox reaction can be expressed such as to depict actual gain or loss of
electrons. If electrons are donated, the reaction is an oxidation, while if electrons are
accepted, the reaction is a reduction.
Zn( s ) Zn 2+ (aq ) + 2e
Cu 2+ (aq) + 2e Cu ( s )

Oxidation
Reduction

The processes of oxidation and reduction are spatially separated by the electrolyte with
reduction occurring at one electrode, the cathode, and oxidation at the other, the anode.
In the electrochemical cell, both oxidation and reduction reactions take place at the two
electrodes (as 2 half-reactions) so as not to violate the laws of conservation of matter and
energy. Each electrode is in contact with the electrolyte and at the interface there is an
interchange of ionic to electronic current (or vice versa). Electrolyte is by definition an
ionic conductor, while electrodes are electronic conductors.
Sketch of an electrochemical cell

Galvanic Cell
The electrodes are linked externally through electrically conducting wires, high
impedance meters, electrical shunts, electrical loads, devices, batteries and power
supplies or systems.
When electrode reactions take place by the virtue of a thermodynamic driving force, the
cell is termed a galvanic cell.

Cathode is the positive pole and anode is the negative pole of a galvanic cell.

In galvanic cells, chemical energy embodied in the reactants is converted to electrical

energy.

Technological examples of galvanic cells are sensors, fuel cells, batteries and
supercapacitors. Corrosion of materials is also a result of galvanic action.

Electrolytic Cell
Electrical energy can be supplied using an external power source in order to drive the
electrode reactions in a direction opposing the driving force.
In this cell the anode is made the positive electrode via which current enters the
electrolyte and the cathode is made the negative electrode from where the current exits
out of the cell.

Electrolytic cells are used in charging batteries and supercapacitors and in electroplating,
metal production and electrophoresis.

Electrolytes
Aqueous electrolytes: These are based on salts, acids, bases dissolved in water and they
conduct electricity via a mixture of ions such as H+, OH-, Mz+, Xz- . All ions present in
the aqueous solution contribute to the current but not necessarily by the same amount.
Aqueous electrolytes are extensively used in fuel cells, batteries, sensors, supercapacitors,
electroplating and electrolysis.

Molten Salts: When salts undergo melting they are capable of conducting ions and carry
current.
Large scale application of NaF-AlF3 molten salt saturated with alumina at 1000oC is used
industrially in electrolytic cells to produce over 20 million tonnes per year of metallic
aluminium.
Other halides based on NaCl, KCl, LiCl and MgCl2, CaCl2 are also used in order to
produce the very reactive alkali and alkaline earth metals.
Fuel cells using molten salts of carbonates have achieved a high state of development for
commercial applications.
All ions present in the molten salt system contribute to the current but not necessarily by
the same amount.

Ionic Liquids: These are special class of electrolytes based on organic salts (typically
made up of inorganic anions and large organic cations) that are liquid at or near room
temperature and thus can effectively offer the advantages of molten salts at low
temperatures without the need for water as the solvent as in aqueous electrolytes.
Electrochemical applications in solar cells, metal production, and synthesis of nanostructures and in batteries and supercapacitors are being researched extensively.
Typically, ionic liquids have low vapour pressure and low flammability in comparison
with many organic solvents, and are intrinsically conductive due to their ionic nature.
Ionic liquids can be constituted by combining a cation which can be metal cation (e.g.
Zn2+) or organic (e.g. Tetraalkyl ammonium) with an anion which can be inorganic (e.g.
halides) or organic (e.g. methylsulfates)

Solid Electrolytes: Ion conductors in the solid state exist as an intermediate between
conventional ionic solids and ionic liquids. They have a rigid immobile structure formed
in one sub-lattice through which a component can move relatively freely within another
sub-lattice. Many of the ionic conductors have the potential to be employed in
electrochemical cells, ranging from sensors, fuel cells, supercapacitors and electrolysers
to batteries, electrochemical capacitors and electrochromics, as well as devices with ionsensitive electrodes including pH meters.

Oxygen ion conductors represent the most important class of solid state ionically
conducting materials. Of these, the most widely investigated, and used, solid electrolytes
are based upon ZrO2. The interest in the zirconias, both from the scientific and the
technological viewpoint, has been truly overwhelming over the last five decades, and
there are now countless practical applications relying on this material. ZrO2 when doped
with aliovalent oxides, such as Y2O3, CaO and MgO, acquires ionic conduction for
oxygen ions over a wide range of temperature and partial pressure of oxygen.
Pure zirconia undergoes two structural transformations on heating (or the reverse on
cooling):
monoclinic tetragonal cubic ,
1170C

2340C

Melting takes place at approximately 2680 C. (See Phase Diagram in the next page.)
During transformation from the tetragonal to the monoclinic phase there is a large
specific volume change of 5 %, resulting in cracking of a pure zirconia monolith
rendering the material useless for most applications. The high-temperature cubic fluorite
phase of zirconia can be partially or fully stabilised to lower temperatures by the
substitution of a portion of the Zr4+ cations with lower valent cations like Mg2+, Ca2+,
Y3+, Sc3+ or trivalent rare earth (RE) metal cations. This substitution is possible because
ZrO2 can form solid solutions with the respective divalent or trivalent oxides.
These aliovalent dopants stabilise the fluorite structure and thereby avoid the destructive
tetragonal-to-monoclinic transformation. In addition, the dopants introduce vacancies in
the oxygen ion sites due to their lower valences. When yttria is used to stabilize zirconia,
it is called yttria-stabilized zirconia (YSZ).

Phase Diagram
The introduction of yttria into zirconia and the formation of a solid solution can be
described as:
/

Y2 O3 2YZr
+ 3OO
+ VO

Oxygen ion conduction in stabilised zirconia occurs via these vacancies, because oxygen
ions, OOx , are able to exchange sites with adjacent oxygen vacancies, VO.. . Thus the
oxygen ion motion can be considered to be equal and opposite to the vacancy motion.
As the dopant concentration is increased, the number of oxygen vacancies will increase
according to the stoichiometric relationship:

[ ] [ ]

/
2 VO = YZr

As can be seen from the figure below, the conductivity in stabilised zirconia first
increases with increasing dopant content, before reaching a maximum, beyond which the
conductivity then decreases.
The reason for this maximum is that above a critical vacancy concentration defect
clusters are prevalent, decreasing the mobility of the oxygen vacancies and thus
decreasing the conductivity. The composition that displays the conductivity maximum in

stabilised zirconia corresponds to the minimum amount of dopant required to fully

stabilise the cubic phase. At a temperature of 1000 C, which represents a typical fuel cell
operating temperature, the conductivity maximum occurs near 8 mol% Y2O3.

Conductivity vs mol % dopant

The tetragonal phase within a partially stabilised zirconia (PSZ) can transform to the
monoclinic phase under mechanical stress. Energy absorbed through the corresponding
increase in volume of 3 to 5 % arrests crack growth resulting in toughening of the
ceramic.
Thus, a partially stabilised zirconia containing the cubic and the tetragonal phases at
typically less than 8 mol% yttria combines high ionic conductivity with high toughness
and thermal shock resistance. A fully tetragonal phase is formed in the 2 to 3 mol% Y2O3
system in the temperature range from 1200 to 1500 C, commonly known as tetragonal
zirconia polycrystals (TZP). The transition to monoclinic can be completely suppressed at
temperatures below 500 C, provided the grain size is less than 300 nm, which results in
a strong and tough material. At less than 50 nm the material is extremely tough while
retaining hardness and strength.
Within the solid solution range, the vacancy concentration in stabilised zirconia is
determined by the dopant concentration. At higher temperatures and low partial pressure
of oxygen, electrons may appear as a result of the non-stoichiometric reactions between
lattice and gaseous oxygen:
1

OO
VO + O2(g) + 2e /
2

with equilibrium constant K expressed as:

K = [e / ] 2 [VO ]p O

12
2

where pO2 is the partial pressure of oxygen. At high partial pressure of oxygen, electron
holes may appear:
1

VO + O2(g) OO
+ 2h
2
with equilibrium constant given by:

K=

[h ] 2
[VO ]pO

12
2

The conductivity is given by the equation:

= charge concentration of charge carrier mobility
Since electronic mobility is usually much higher than ionic mobility, typically by nearly
about three orders of magnitude, the ionic conductivity is dominant only when the ionic
defect concentration is very large relative to the electronic defects.
The ionic transference number is defined as the ratio of ionic conductivity to total
conductivity. In the case of an oxygen ion conductor, such as YSZ, the oxygen ion
transference number t O 2 is defined as:

t O 2 =

O 2

O 2 + e / + h
For a given temperature there is a range of oxygen partial pressure values within which
ionic defects dominate. This renders oxygen ions the majority charge carrier and oxygen
ion conductivity independent of oxygen pressure.
O 2 = const
The ionic (or electrolytic) domain is defined by the range of oxygen partial pressures for
which tO 2 0.99. This is represented in Figure shown below which has been calculated
on the basis of numerical values typical for stabilised zirconia. Oxygen ion, electron and
hole conduction are all activated processes with typical activation energies in 8 mol%
YSZ of 0.85, 3.88 and 1.67 eV, respectively. Due to their higher activation energies, the
electron and hole conductivities increase more than the ionic conductivity as temperature
rises. This causes the width of the electrolytic domain to diminish, as is shown
schematically. Knowledge of the electrolytic domain is important in order to be able to
use the oxygen ion conductor as a solid electrolyte in sensors and fuel cells.

T, K

Hole conduction

Log
pO2
(atm.)

tion = 0.99

Ionic Domain
tion = 0.99
Electronic
conduction

1/T, (per K)

10

Separator: In addition to the electrodes, the two other constituents that are required for
electrochemical reactions to be usefully harnessed are the electrolyte and the separator.
The electrolyte is an ion conducting material, which can be in the form of an aqueous
system, an ionic liquid, an organic solvent containing a soluble salt, a molten salt, or a
solid electrolyte, while the separator is a membrane that physically prevents direct
contact between the two electrodes and allows ions to pass through; it therefore ensures
electrical insulation for charge neutralization in both the anode and cathode once the
reaction is completed. A separator is soaked in the electrolyte when liquid electrolyte is
used.

11

Electrochemical Reactions
The general expression for a reduction reaction is
Ox + Z e- = Red
Both Ox and Red may be positive, neutral or negative species.
The standard reduction potential Eo is a measure of how easily a species can gain (or
loose) electrons.
Table Standard Electrode Potentials in Aqueous Electrolyte at 298K (written as reduction
reactions by convention)
Reaction

E0 / V

Li+ + e Li
Na+ + e Na
Mg2+ + 2e Mg
Mn2+ + 2e Mn
MnO2 + 2H2O + 4e Mn + 4OH
2H2O + 2e H2 + 2OH
Cd(OH)2 + 2e Cd + 2OH
Zn2+ + 2e Zn
Ni(OH)2 + 2e Ni + 2OH
Fe2+ + 2e Fe
Cd2+ + 2e Cd
PbSO4 + 2e Pb + SO42
Ni2+ + 2e Ni
MnO2 + 2H2O + 4e Mn(OH)2 + 2OH

-3.10
-2.71
-2.36
-1.18
-0.98
-0.83
-0.82
-0.76
-0.72
-0.44
-0.40
-0.35
-0.26
-0.05

2H+ + 2e H2

0.00

Ag2O + H2O + 2e 2Ag + 2OH

Cu2+ + 2e Cu
O2 + 2H2O + 4e 4OH
2NiOOH + 2H2O + 2e 2Ni(OH)2 + 2OH
NiO2 + 2H2O + 2e Ni(OH)2 + 2OH
MnO42 + 2H2O + 2e MnO2 + 4OH
Ag+ + e Ag
O2 + 4H+ + 4e 2H2O
PbO2 + 4H+ + 2e Pb2+ + 2H2O
PbO2 + SO42 + 4H+ + 2e PbSO4 + 2H2O
F2 + 2e 2F

+0.34
+0.34
+0.40
+0.48
+0.49
+0.62
+0.80
+1.23
+1.47
+1.70
+2.87

12

The Standard Hydrogen Electrode (SHE)

H2 of pressure 1 atm is bubbled into an HCl (aq) solution at a concentration of 1M onto a
high surface area Pt.
By definition, Eo(SHE) = 0 V
The very electropositive metals, such as Li, Mg, Mn will directly react with water
decomposing it and produce hydrogen and thus thermodynamically they are unstable as
electrodes in aqueous electrolytes.

The standard potential of a half-reaction is reported with respect to the SHE in an

aqueous solution, whereby the species are in their standard states defined by
1M for soluble species
Saturation for slightly soluble species
1 atm. Pressure (101325 Pa) for any gas
Pure substance in stable form for a metal
Pure substance in stable form in contact with the metal for other solids
The overall cell reaction (redox reaction) can be expressed by combining 2 half reactions
with the more +ve potential undergoing reduction; the one with the less +ve potential will
be reversed and proceed as oxidation.

Nernst Equation
When the species are not in their standard state, we can calculate the electrode potential
by using the Nernst Equation.
The Nernst Equation for the reaction:
Ox + Z e- = Red
is given by:

13

E = Eo

2.303RT
[Re d ]
log
zF
[Ox]

Reference Electrode
Since the standard hydrogen electrode may not be a convenient reference electrode in
practical usage, other reference electrode systems have been developed for practical use
in aqueous systems.

Ag/AgCl electrode:
Cl-(of defined concentration) | AgCl(s) | Ag(s)
The Cl- concentration is fixed using a saturated aqueous solution of KCl
The electrode reaction for this reference electrode is:
AgCl + e- = Ag + Cl-

Eo (298K) = +0.23 V

Using the Nernst equation:

E = Eo

2.3.3RT
log[Cl ]
F

The electrode potential with a solution of KCl (usually saturated) is given by

E = +0.197 V at 298K.
Saturated calomel electrode (SCE)
Cl (defined ) | Hg 2 Cl 2 ( s) | Hg (l )
The Cl- concentration is fixed using a saturated aqueous solution of KCl
The electrode potential a solution of KCl (usually saturated) is given by
E = +0.244 V at 298K.

14

Concentration Cells:

In an electrochemical cell, the cell potential can arise simply by using 2 different
concentration of a selected substance at the 2 electrodes. If the electrodes are connected
in the external circuit a current would flow through the cell system in order to try and
eliminate the concentration difference. [In reality, it is activity difference rather than
concentration difference that will drive the net electrochemical reaction in a
concentration cell]
Concentration cells are very commonly employed in practice. Electrorefining of impure
Cu to pure Cu in an aqueous electrolyte is a concentration cell. Galvanic cells using a
YSZ solid electrolyte separated by different oxygen partial pressures at the anode and the
cathode is a concentration cell as shown below.
Ni, NiO | YSZ | Fe, FeO

15

Electrode Kinetics
Interface
When a metal electrode is in an electrolyte, the charge on the metal will attract ions of
opposite charge in the electrolyte, and the dipoles in the solvent will align. This forms a
layer of charge in both the metal and the electrolyte, called the electrical double layer, as
shown in Fig below. The electrochemical reactions take place in this layer, and all atoms
or ions that are reduced or oxidized must pass through this layer.
Thus, the ability of ions to pass through this layer controls the kinetics, and is therefore
the limiting factor in controlling the electrode reaction. The energy barrier towards the
electrode reaction, described as the activation energy of the electrochemical reaction lies
across this double layer.

Electrode Kinetics
When an electrode is not at equilibrium an overpotential exists, given by

= E Eo,
where is the overpotential, E is the actual potential, and E0 is the equilibrium potential.
Overpotential is used synonymously with polarization. Electrode kinetics is described by
Tafel equation at each of the electrode:
Anode:
A = EA E o

A = a A + b A ln i A
16

or in terms of exchange current density io (which reflects the rate at which equilibrium is
achieved for a given electrode/electrolyte system):

A = b A ln(i A / io )
and similarly for the cathode, substitute A with C.

Space for a typical Tafel plot:

Thus for an applied potential, the current density, i, can be found from the Tafel plot in an
electrolytic cell when the battery is being charged or vice versa in a galvanic cell as in a
battery being discharged.

At very high currents a limiting current may be reached as a result of concentration

overpotential, C, restricting mass transfer rates to the diffusion rate of the electroactive
species. A limiting current arises which can be derived from Ficks first law of diffusion
under the condition that the electrode surface is depleted of the ion and the recovery of
the ion concentration is limited by ion-transport through the electrolyte diffusion
boundary layer.
The limiting current is diffusion limited, and can be determined by Ficks law of
diffusion as, where iL is the limiting current density over a boundary layer:

17

iL =

zFDC

where iL is the limiting current density over a boundary layer, D is the diffusion
coefficient of metal cations in the electrolyte (or chemical component in the electrode in
some other situation), C is the concentration of metal cations in the bulk electrolyte, and
is the thickness of the boundary layer.
Typical values for deposition for Cu from Cu2+ for example would be:
D = 2x 10-9 m2s-1,
C = 0.05x 104 kg m-3,
= 6x 10-4 m, which gives
iL = 3.2 x 102 A m-2
The concentration overpotential thus represents the difference between the cell potential
at the electrolyte concentration and the cell potential at the surface concentration because
of depletion (or accumulation) at high current densities, given by

C (conc.) =

i
2.303RT
ln(1 )
zF
iL

Space for a Tafel curve showing this diffusion limiting of the current:

18

Electrochemical Sensors
Electrochemical principles form the basis of applying solid state ionic conductors in
chemical sensors for monitoring and/or controlling chemical components in gaseous,
liquid and solid systems. Solid electrolytes interfaced with suitable electrodes can directly
and quantitatively transduce the chemical activity of the species to be sensed into a
readily measurable electrical quantity. Electrochemical sensors are used either in the
potentiometric or in the amperometric mode. In potentiometric sensors, the open
circuit potential difference between the anode and the cathode, also termed electromotive force, emf, is measured at zero current with a high impedance voltmeter. One of
the electrodes contains the species to be sensed, the other is the reference electrode, and
the emf can be related directly to the unknown activity of the target component. In
amperometric sensors, the current is measured under an applied voltage between anode
and cathode. This current can be related to the activity of the target component.

Oxygen Sensor
The commercialized oxygen sensor is composed of a partially stabilised zirconia thimble
as the oxygen ion conducting solid electrolyte and porous coatings of platinum - rhodium
on both sides as the electrodes. As described earlier, 3 mol% YSZ, corresponding to a
mixture of tetragonal and cubic phases, provides optimum mechanical and electrical
properties. The electrodes are applied to the solid electrolyte by thermal evaporation,
sputtering or chemical deposition, followed by thermal treatment. During sensor
operation both electrodes are hermetically sealed from each other. One electrode is
exposed to the test gas, the other electrode is exposed to air serving as the reference.
A heater brings the sensor to its operating temperature, thus called Heated Exhaust Gas
Oxygen Sensor (HEGO). A porous layer of thickness 50 to 300 m around the sensing
electrode protects the sensor from mechanical damage. The layer also acts as a diffusion
barrier for the gas and ensures thermal equilibration of the gas before it reaches the
electrode. The layer is made from MgAl2O4, Al2O3, ZrO2 or a combination thereof, and is
produced with organic pore forming substances. A schematic diagram is shown below:
The oxygen sensor (also referred to as a probe) operates as a galvanic oxygen
concentration cell:

(+) Pt, O2 (ref) | YSZ | O2 (test), Pt (-).

test
, and the
The test chamber contains the sample gas of oxygen partial pressure pO
2

ref
reference chamber contains air, rendering the reference oxygen partial pressure pO
2

equal to 0.21 atm. The emf generated by the difference in oxygen partial pressure is given
by the Nernst equation:

19

test
pO
2.303RT
emf =
log 2
ref
4F
pO
2

where R is the universal gas constant, T is the absolute temperature, and F is the Faraday
constant. The high catalytic activity of the platinum and rhodium helps establish
thermodynamic equilibrium at both electrodes. The oxygen partial pressure difference
between the exhaust gas and the air causes opposite reactions at both electrodes. Under
operating conditions, the working electrode is the anode and the electrode reaction is:
2O 2 (YSZ ) = O2 (test ) + 4e

The reference electrode is the cathode and the electrode reaction is:
O2 ( reference) + 4e = 2O 2 (YSZ )
The stoichiometric point of an automotive internal combustion engine is at an air-to-fuel
mass ratio of ~14.7, ensuring complete reaction of both the fuel and the oxygen. The
air/fuel ratio, A/F, is commonly expressed in terms of the normalised quantity lambda, :
=

operating A/F
stoichiome tric A/F

20

The stoichiometric point is at = 1, and here the equilibrium partial pressure of oxygen
in the exhaust gas varies between 10-20 and 10-2 atm, i.e., from slightly fuel-rich to
slightly lean-burn. This sharp change in oxygen pressure produces a large change in the
emf.
Figure (below) shows the resulting emf curves relative to the normalised air/fuel ratio for
a fixed temperature. This response characteristics makes the sensor ideal for closed-loop
control of the automotive internal combustion engine centred at = 1.

10-1

1.0
pO2
Calculated
sensor voltage

10-6
10-11

0.6

0.4

pO2 (bar)

V Nernst (V)

0.8

10-16

0.2
10-21

0
0.90

0.95

1.00

1.05

1.10

Normalized air fuel ratio

Lowering the concentrations of pollutant gases CO, hydrocarbons (HCs) and NOx from
automobile emissions is achieved by the use of three-way catalysts (TWC) placed
upstream in the exhaust gas. When operated at stoichiometric air/fuel ratio, the TWC can
simultaneously oxidise CO and HCs to CO2 and H2O and reduce NOx to N2, and in this
way convert pollutant gases into innocuous gases. The concentration of gases as a
function of air/fuel ratio is shown below.

The catalyst is deposited on a CeO2 layer with oxygen storage capacity such that oxygen
can be stored when the exhaust gas is slightly lean and released when it is slightly rich.
Keeping inside a narrow window around the stoichiometric point is therefore critically
important in the engine management.

21

<1

=1

>1

CO2

12

Hydrocarbons

CO, CO2, O2 or H2 (vo l%)

Stoichiometric
mixture =1
4

NO

CO

NO, hydrocarbons (x1000 ppm)

10

H2
2

O2

10:1

12:1

14:1

16:1

18:1

Air to fuel ratio (wt)

22

Batteries
Introduction
There are two main types of batteries: primary and secondary batteries. In primary
batteries the chemical energy stored in the cell is such that it can be used only once to
generate electricity, i.e. once the cell is fully discharged it cannot be of further use.
In secondary batteries the reverse redox reaction (also referred to as electrolysis and
charging) can occur when the current is applied at a potential higher than the cell
potential (Ecell) and the battery can be used reversibly many times. During charging,
electrons flow to the anode through the external circuit and cations from the cathode
diffuse through the electrolyte.

Primary Batteries
Primary batteries are not easily or safely rechargeable, and consequently are discharged
and then disposed of. Many of these are dry cells cells in which the electrolyte is not
a liquid but a paste or similar. The cell electrochemical reactions are not easily reversible
and the cell is operated until the active component in one or both the electrodes are
exhausted. Any attempt for reversing the reaction via recharging in a primary cell is
dangerous and can cause the battery to explode.
The electrical resistance in primary cells is usually high, thus, even if charging was
possible it would be a slow process; at normal practical charging rates, a large proportion
of the current would have been likely dissipated as heat, causing further safety hazards.
Primary batteries are therefore designed to operate at low currents and have a long
lifetime. Generally primary batteries have a higher capacity (Ah/Kg), a higher specific
energy (Wh/Kg) and a higher initial voltage than secondary (rechargeable) batteries of
comparable chemistries. They are used in portable devices, toys, watches, hearing aids,
medical implants. The commercially used primary batteries are shown below.

23

Primary battery chemistries in use

System
Cathode/Anode

Nominal Specific
Cell
Energy
Voltage(V) (Wh/Kg)

Advantages

Disadvantages

Applications

Carbon/Zinc

1.50

65

Low energy
Lowest cost;
Torches; radios;
density; poor lowvariety of shapes
electronic toys and
temperature
and sizes
games;
performance

Mg/MnO2

1.60

105

Higher capacity High gassing on

Military and aircraft
than C/Zn; good
discharge;
receiver-transmitters
shelf life
delayed voltage

Zn/Alk/MnO2

1.50

95

Zn/HgO

1.35

105

Cd/HgO

Zn/Ag2O

Zn/Air

Li/SOCl2

0.90

1.50

1.50

3.60

Higher capacity
Personal stereos;
than C/Zn; good
calculators; radio;
Moderate cost
low-temperature
T.V
performance
High Energy
Hearing aids;
Expensive; energy
density; flat
pacemakers;
density only
discharge; stable
photography; military
moderate
voltage
sensors/detectors

45

Good high and

low-temperature
performance;
good shelf life

Expensive; low
energy density

130

High Energy
density, good
high rate
performance

Expensive (but
cost effective for
niche
applications)

Watches;
photography;
missiles; Larger
space applications

290

High Energy
density; long
shelf life

Dependent on
environment;
limited power
output

Watches; hearing
aids; railway signals;
electric fences

300

High Energy
density; long
shelf life

Only low to
moderate rate
applications

Memory devices;
standby electrical
power devices;
medical devices

Li/SO2

3.00

280

Li/MnO2

3.00

200

High energy
High-cost
density; best
Military and special
pressurized
low-temperature
industrial needs
performance;
system
long shelf life
High energy
density; good Small in size, only Electrical medical
low-temperature
low-drain
devices; memory
applications
circuits; fusing
performance;
cost effective

24

Secondary Batteries
In the secondary battery market, several new cells have been introduced just within the
last two decades, for example, the Ni-MH cell (1990), Li-ion cell (1991), rechargeable
alkaline cells (1992), Li polymer (1999), and also the concept of mechanically
rechargeable Zn-air batteries (2001). The new batteries, especially those based on the Li
chemistries have not only met some of the existing demand, but can be said to have
revolutionized the battery market by accelerating demand for laptops, mobile phones and
cordless hand held tool products.

An inspection of Fig. above clearly reveals that with time, the specific energy (Wh/Kg)
and the energy density (Wh/litre) have continued to grow as batteries advance. It is this
combination of high values of Wh/Kg and Wh/litre that have been the key factors
heralding this rapid growth. The number of batteries produced each year is staggering.
The relatively newcomers, Li-ion batteries, alone are produced in quantities exceeding
1.2 billion cells per year. The global market anticipated for the year 2015 is shown
below:

Table Global Battery Market Forecast for 2015

Type of Battery
Primary

Carbon Zinc
Alkaline
Others
Secondary

Lead Acid
Ni-Cd / Ni-MH and others
Li

Global Demand in US$, 150 billion

Primary Total : 40%
8%
22%
12%
Secondary Total: 60%
28%
12%
14%

25

Li-ion Batteries
In a Li-ion cell, both electrodes are based on insertion materials which can insert
and de-insert lithium reversibly over many cycles. The most efficient secondary battery,
though, is the lithium-ion battery which was commercially introduced by Sony in 1991.
This cell chemistry included a LiCoO2 cathode and a carbon anode, whose potential after
being fully charged is 4.2 V. The reversible reaction occurs by the intercalation reaction
of lithium ions between the LiCoO2 and carbon frameworks in a non aqueous liquid
organic electrolyte (1M lithium hexafluorophosphate (LiPF6) in 1:1 weight mixture of
EC:DEC (ethylene carbonate : diethyl carbonate)). The face-centered cubic structure of
LiCoO2 met the requirement of small volume changes (about 2%) during the Li-insertion
and de-insertion that took place upon electrochemical cycling. The delithiated state is
believed to maintain its layered structure, which is similar to a hexagonal close-packed
structure.
The cell potential arising from the voltage difference between delithiatedLiCoO2
and lithiatedcarbon is large making it a high energy density battery. Graphite is a
suitable anode material since its layered structure with hexagonal vacant sites allows
lithium ions to be inserted with a very small volume change taking place (graphite
interlayer expansion, which is about 11%) and can return back to its initial volume after
the de-lithiation process. Graphite and other carbon anode materials can readily achieve
this at a potential which is still relatively close to that of pure Li. While the rate of
charging, cyclability and safety are significantly improved with a carbon anode, in
comparison with a pure Li, the self-discharge rate is much higher.
The gravimetric capacity of this cell is 372 mAh/g and the corresponding
volumetric capacity is 800 mAh/dm3. However, a safety concern arises from the high
reactivity between the lithium and the organic electrolyte in the deep charging state and
may result in fire initiation. Use of a gel polymer electrolyte can prevent such risks. This
gel electrolyte is used as a very thin film in order to overcome the resistance arising from
the low conductivity of the polymer.
A typical Li-ion battery can be schematically represented as shown in Figure
below, while the working principle is depicted in the next Figure. In addition to the Co
based compounds, the Li cathode can comprise of other chemistries based on Mn, P, Ni
and Fe and various combinations.

26

27

Fuel Cells
A fuel cell is an electrochemical device that is able to continuously convert the chemical
energy embodied in a fuel and an oxidant directly into electrical energy. The conversion
to electrical energy takes place silently without combustion. Fuel cells are classified
according to the type of electrolyte employed. The most common types are described in
the Table below:
Type
Alkaline Fuel Cell (AFC)
Phosphoric Acid Fuel Cell
(PAFC)
Polymer Electrolyte
Membrane Fuel Cell (PEM)
Molten Carbonate Fuel
Cells (MCFC)
Solid Oxide Fuel Cell
(SOFC)

Electrolyte
KOH (aq)
H3PO4(aq)

Operating Temperature, oC
0 - 150
200

Nafion polymer

0 - 120

(K,Li)2CO3

550-700

YSZ

900-1000

Polymer Electrolyte Fuel Cell

The most widely used polymer membrane in PEM fuel cells is Nafion, produced by
DuPont Company and readily available in the form of a membrane. It is a semicrystalline co-polymer tetrafluorethylene and sulphonyl fluoride vinyl ether in a molar
ratio of 7:1, with typical equivalent mass of around 1200 g. The hydrophobic regions
dominate the structure, but hydrophilic sulphonate groups are placed in close proximity
to the tetrafluoroethylene backbone and act as cross-links in the matrix, endowing the
material with rigidity, inertness and insolubility.
Nafion can absorb a large quantity of water and its conductivity for protons is dependent
upon the water content, and thus the relative humidity, surrounding the membrane.
Thinner membranes have higher conductivity but lower physical strength and higher
permeability for the fuel. Lower strength can result in faster degradation and poor life.
Higher permeability is responsible for fuel crossover and loss of electrochemical
efficiency.

Electrochemical Reactions:
Considering hydrogen as the fuel and oxygen gas as the oxidant, the following reactions
take place:
Anode:

28

H2 (g) 2 H+ + 2 eCathode:
O2 + 2 H+ + 2 e-

H2O

Overall Cell Reaction:

H2 (g) + O2 H2O (l)
At 298 K, the standard free energy change for the overall reaction is given by:
Go = -237,000 J = - 2 F Eo
Thus the maximum cell potential or the open circuit potential (at zero current) can be
calculated as 1.23 V.
In a fuel cell the useful energy output is electrical energy produced and the energy input
is the enthalpy of hydrogen (286,000 J/mol). If all the free energy can be converted to
electrical energy, then the maximum fuel cell efficiency at 298 K is given as:
= Go / Ho = 237,000 / 286,000 = 0.83 = 1.23/ 1.48
where the thermoneutral potential is 1.48V.
Efficiency is reduced by many factors, such as crossover of fuel from anode to cathode
via the electrolyte; unreacted fuel passing out of the anode zone; parasitic reaction of the
fuel with contaminants such as oxygen.
The mechanism for oxidation of hydrogen takes place by adsorption on a suitable
electrocatalyst such as Pt on which the overpotentials are low and exchange current
density high with Nafion (0.1 A cm-2). Presence of CO (in ppm levels) in the fuel, can
poison the catalyst by adsorbing strongly and blocking the active surface. CO tolerance is
improved when Pt is alloyed oxophilic elements such as Sn, Mo, W or Ru.
The oxygen reduction reaction is a lot more sluggish with low exchange current density
even on the best electrocatalyst Pt ( 6x10-6 A cm-2) and high overpotentials. This reaction
is the major cause of low energy conversion in both PEM and Aqueous Electrolyts-based
fuel cells. Problem arises from incomplete conversion to water by the 4-electron pathway
per mole of oxygen (equation 25) rather losses from conversion to H2O2 by 2-electrons
pathway and formation of other intermediates such as oxygen superoxide ions O2- and
O22-.
Despite major research on Pt, the oxygen reduction reaction is still the major limiting
factor in PEMFC. In any event Pt is scarce even at the high price it commands; focus of
research is shifting towards developing non-noble electrocatlaysts for both anode and

29

cathode reactions. Use of metal particles (such as Pt, Pd, Au, Cu, Ni, Ta) and metal
carbides (WC) on nanoparticles of oxides or carbon have shown to be promising avenues.
Carbides also display CO tolerance.
Fuel cells electrode reactions also follow polarization curves similar to that of batteries.
The actual cell voltage is always less than the open circuit voltage (ocv). The
overpotential losses are dependent upon the operating current density. The anode
potential will move to a more positive value, thus polarizing towards the cathode while
the cathode potential will move towards the anode to a more negative value.
In general, as described previously for batteries
Ecell = Erev a c I R
When Pt is used, it is normally supported on C black. C black is made of nanoparticles of
amorphous (and semi-crystalline) spheres aggregated into a network of highly porous
structure. Aggregates can also form stable agglomerates. The structure permits flow of
electrolyte and provides diffusion path for the gaseous fuel and the oxidant. CNTs are
also being investigated as possible support materials and also for holding hydrogen
within the tubes as well as intercalated in the graphitic structure.
A schematic
Diagram of
Carbon black
Structure (each C
Nanopaticle is 5
-10 nm in size)
Surface areas >
1000 m2/g
are readily
available.

PEM fuel cells are also developed using liquid fuels such as methanol, ethanol or formic
acid.
The key performance measure of a fuel cell is the voltage output as a function of
electrical current density drawn, or the polarisation curve shown below in Fig. below.

30

Current density [A cm-2]

Schematic fuel cell polarisation and power density curves

Solid Oxide Fuel Cells (SOFC)

The most commonly used electrolyte in SOFC is yttria-stabilized zirconia (YSZ).
SOFC electrodes are typically made of mixed electronic and ionic conducting materials,
thus both electrons and ions can flow through them. In the figure below for anode as an
example, ions coming from the electrolyte flow through the anode thus combining with
H2 and releasing electrons at the so triple-phase-boundary (TPB). Consequently electrons
flow towards the anodic current collector.
The TPB concept holds that the H2 oxidation reaction and the oxygen reduction reaction
can only occur at confined spatial sites, called triple phase boundaries, where electrolyte,
gas and electrically connected catalyst regions contact.

31

Diagram showing the triple phase boundary

The most commonly used anode for hydrogen oxidation for YSZ electrolytes is a porous
cermet structure consisting of two interpenetrating and interconnecting networks of Nimetal and Yttrium stabilized Zirconia particles. The gas phase in the pores account for
more than 50 % of the volume. The large internal surface in the porous structure makes it
possible to obtain large external current densities while keeping the local internal current
densities and over potentials low. At the same time the pores enable the H2 molecules to
penetrate all the way into the cermet and the H2O molecules produced to escape out of
the electrode.
The cathode is required to act as an electrocatalyst i.e. promoting the electrocatalytic
reduction of O2 to O2-:
O2 (g) + 4e- 2O2Although several metals, such as Pt and Ag can also act as electrocatalysts for the above
reaction, the most commonly used materials for the cathode are taken from the
perovskites. The most common of all is the perovskite La1-xSrxMnO3- (LSM). This
material demonstrates both ionic and electronic conductivity and thus the electrocatalytic
sites are not restricted to the geometric TPB, but can also exist on the gas-exposed
electrode surface as well, forming an electrochemically active zone, which can in
principle, extend over the entire gas-exposed electrode surface.
The electrical energy converted from chemical energy in the cell, is carried by electrons
to the external circuit, by what are referred to as current collectors. Depending on the cell
configuration, current collectors might also be situated between series cells, which are
then referred to as interconnects. In either case they both serve the same purpose. In the
past platinum has been used due to its high electrical conductivity and excellent adhesion,
however its relative cost has not permitted further consideration for future designs.

32

Until recently, the leading candidate material for the SOFC interconnect was
electronically conducting doped lanthanum chromite, LaCrO3 a ceramic which could
easily withstand the 1000C operating temperature of an electrolyte or air electrode
supported SOFC design. It is typically doped with Sr and Ca in order to improve
electrical conductivity and decrease sintering temperature to help facilitate dense
impermeable ceramic monolith. It is still quite expensive, fragile and can be partially
reduced by the fuel with time. It is desirable to be able to decrease the operating
temperatures of SOFCs to < 700oC, so that high temperature metallic alloys (Cr and/or Ni
based alloys) can be used as interconnects.

Typical Designs:
Tubular Oxide Fuel Cell

Planar Oxide Fuel Cell

ELECTROLYSIS

33

ELECTROWINNING
Extraction of metals from aqueous solutions or molten salts in electrochemical cells - the
metal is plated or deposited on to the cathode (-ve), while the anode is an insoluble
conductor (e.g. a Pb alloy), where a gas such as oxygen or chlorine is evolved
From Aqueous Solutions
electrochemical cell:

Copper sulphate in aq. solution is decomposed in an

At cathode:
Cu2+ +2e = Cu

EO = + 0.34 V + RT/2F ln [Cu++]

At anode:
H2O = 1/2 O2 + 2H+ + 2e

EO = + 1.23 V - RT/F pH

Net reaction for electrowinning copper is:

CuSO4(aq) + H2O = Cu + 1/2 O2 + H2SO4(aq)
G = 221.6kJ; E = -1.2V
1.2V is the minimum potential required to bring about the electrochemical reaction as
shown above. Due to polarisation processes the operating voltages are nearly 2.5 V at a
typical current density of 200 A/m2.
The actual potential required is = 1.2 + A + C + IR
Note: Electrolytic extraction from aqueous solutions is possible for Ni, Co, Cd, Fe, Zn
and Mn, by decomposing their salts in aq solutions without the danger of decomposing
H2O to form hydrogen gas at the cathode

If the reversible electrode potential required to deposit a metal is < - 1 V (or Total
potential > 3 V), the possibility of evolving hydrogen at the cathode increases

34

ELECTROREFINING:
Electrorefining of copper anode consists of applying an electrical potential between the
copper anode (+ve) and a starter sheet (pure Cu, stainless steel or Ti) as the cathode, both
immersed in a cell containing an acidified CuSO4 solution
Overall Cell Reaction:
Cu (anode, 99.4 %) = Cu (cathode, 99.999 %)
G = 0 and Emin = 0 V

E(actual) = 0.3V to overcome the resistance of the electrolyte and the external circuit +
overpotentials to carry out the reactions at reasonable rates
Typically, I = 200 A/m2 and Energy consumption = 300 KWH per tonne of Cu deposited
Au, Ag, Pt and other precious metals do not dissolve in the electrolyte and are collected
in the anode slimes
S, Se, Te, Pb and Sn are also collected in the anode slimes
As, Bi, Co, Fe, Ni and Sb dissolve in the electrolyte, but do not deposit in the cathode and
are removed by purification of the electrolyte

35

ELECTROWINNING OF ALUMINIUM:
Reactive metals such as Al, Mg, Li, Ca, Na, K etc cannot be deposited from their salts in
aqueous solutions but are deposited from their fused salts
Bauxite ore is purified in Bayer's process by leaching with NaOH(aq) in order to produce
pure Alumina for electrowinning Al
Alumina can be dissolved up to 8% in a fused salt of cryolite NaF-AlF3 at 1273K and
electrochemically decomposed:
Al2O3(l) = 2Al(l) + 3/2 O2 (g)
G (1273K) = 1279 kJ E(min) = -2.2V

The molten electrolyte is covered with a crust of alumina which acts as a reservoir of feed
as well as insulation
Both the anode and the cathode is made up of graphite - the graphite anode consumed
during the process as a result of oxidation with oxygen evolved at the anode, which leads
to a reduction in the min. potential required:
Al2O3(l) + 3/2 C = 2Al(l) + 3/2 CO2 (g)
for which G (1273K) = 686 kJ E(min) = -1.18 V;
E(total) = 6 V (due to and IR losses)
Primary Al production is a power intensive process (17 KWH/Kg of Al)

36

Photocatalytic Redox Reactions

In photocatalysis, an electron in the valence band is excited to the conduction band (see
Figure below) if light of energy greater than the band gap is provided to the semi
conductor. This excitation creates charge carriers, electron and holes in CB and VB
respectively. The charge carriers migrate to the surface of the photocatalyst where the
redox reaction takes place with adsorbates. In an aqueous environment, water is oxidized
by the hole which generates powerful oxidizing agents OH, called hydroxyl free radicals
(OH) which can readily oxidize organic compounds accompanied with mineralization,
and evolution of CO2 and H2O. The standard electrode potential values, which determine
the strength of oxidants, are given for OH relative to the other common oxidant in the
table below.

The excited electrons in the conduction band are trapped by dissolved oxygen in water
which results in the formation of super oxide anion (O2) by electrochemical reduction.
The different type of redox reactions which can take place are shown in reactions below.
The super oxide anion (O2) can further react with H+ which form hydroperoxyl radical
(OOH) which can further react to produce H2O2.
Photochemical and Redox Reactions

TiO2 + hv hVB+ + eCB

H2O + hVB+ OH + H+

O2 + eCB
O2

OH + *pollutant H2O + CO2

+

O2 + H OOH

37

OOH + OOH H2O2 + O2

O2 + *pollutant CO2 + H2O

OOH +* pollutant CO2 + H2O

*Pollutant here refers to organic compounds.

Oxidant

Reduction potential (Eo )/V

OH (Hydroxyl radical)

2.8

O3 (Ozone)

2.07

H2O2 (Hydrogen peroxide)

1.77

HClO (Hypochlorous acid)

1.49

Cl2 (Chlorine)

1.36

Standard electrochemical reduction potentials of common oxidants vs SHE at 298K

During photocatalysis, the positions of both conduction band (CB) and valence band
(VB) of a photocatalyst play important roles, denoting the relative power of electrons for
photo-reduction and that of holes for photo-oxidation. Using photolysis of water to H2
and O2 as the example to understand the reduction and oxidization power respectively,
the relative position of the CB and VB are considered.
The CB position must be above the H+ ion/ H2 redox couple level in the electrochemical
series for reduction to take place and in similarly the VB position must be below the O2/
H2O redox level in the electrochemical series for oxidation reaction to take place. A
schematic showing the position of CB and VB for different semiconductors with respect
to H+/H2 and O2/H2O is shown in Figure below. Some metal oxides are unsuitable for
producing H2 in an aqueous system, due to the mismatch of their CB and VB with respect
to the position of H+ / H2 and O2/H2O from the electrochemical series.

38

Valence and conduction bands for a number of semiconducting materials on

a potential scale (V) versus the standard hydrogen electrode (SHE). Redox
potentials for the water-splitting half reactions are indicated by the dotted
red lines. In order for a semiconductor to be an effective catalyst its
conduction band energy should be higher than the H2 producing reaction
potential and its valence band energy should be lower than the O2 producing
reaction potential

39

C2 - Examples Class
1. Pure NiO is a p-type semiconductor which forms vacancies on the cation sub-lattice in
a metal deficient Ni1-xO (where x = 0.001 at 600K). Show that electrical conductivity of
nickel oxide will vary as pO1 /26 . The holes are 100x more mobile than the Ni vacancy at
600K. What is the ratio of ionic to electronic conductivity?
What will be the effect of dissolving (a) 0.01 mol % of Li2O; (b) 0.01 mol % of Cr2O3 in
NiO (c) Over oxidising NiO such that some of the Ni appear to be in Ni3+ state ?
In a NiO-0.01 mol % Cr2O3, polycrystalline sample with an average grain size of 10 nm,
the effective Ni vacancy concentration was found to increase by an order of magnitude.
Discuss the implication of this finding.
2. Electrochemical cells are divided into electrolytic cells and galvanic cells.
What is the characteristic feature of an electrolytic cell, and what is the characteristic
feature of a galvanic cell? For each type of cell, name two examples that are of practical
relevance.
Tin is used as a coating on iron to improve corrosion resistance of the iron component.
The electrochemical series gives the following standard reduction potentials for the
Sn2+/Sn and the Fe2+/Fe redox couples: E 0

Sn

2+

/ Sn

= 0.136 V ; E 0

Fe 2+ / Fe

= 0.440 V .

When combining both half-cells, what is the overall cell reaction, what is the standard
cell potential, and what polarity do the two metal phases adopt?
What is the molar Gibbs free energy of the cell reaction under standard conditions, and
what is the equilibrium constant? Which concentration ratio of the two types of ions
would be required in order to generate a cell potential of 0 V? (assume unit activity
coefficients)
[T = 298 K , R = 8.314 J mol-1 K-1 , F = 96500 As mol-1]
3. Impure Cu (99.4 wt%) is electrorefined at 298 K to a pure Cu (99.999 wt%) in an
aqueous acidified electrorefining cell containing 1M H2SO4 (aq) and 1M CuSO4 (aq)
electrolytic solution at a current density of 200 A m-2. The surface area of the electrode is
1 m2. Answer the following using the Data given below:
(a) Calculate the reversible cell potential
(b) Calculate the applied cell potential required for sustaining a current density of 200 A
m-2.

40

(c) Discuss the fate of the following impurities present in the impure anode: Ni, Pb, Ag
and Au and explain why electroefining can help produce very pure copper
[40%]
(d) Can hydrogen or oxygen be evolved at the electrodes?
[Tripos 2014]
Data: (all data specified at 298 K)
Standard Electrode Potentials

Au 3+ + 3e Au

+1.50V

O2 ( g ) + 4 H + + 4e H 2 O

+1.23V

Ag + + e Ag

+0.80V

Cu 2+ + 2e Cu

+0.34V

2 H + + 2e H 2 ( g )

0.00V

Pb 2+ + 2e Pb

-0.13V

Ni 2+ + 2e Ni

-0.25V

The value of the limiting current density for reduction of Cu2+(aq) , i L = 205 A m-2
Tafel slope for oxidation of Cu,

b = 0.295 V per decade

The exchange current density for Cu 2+ + 2e Cu is, io = 1 A m-2

The ohmic resistance, R of the electrolyte is given by 6 x 10-3

41

C2 Question Sheet

1. The following solid-state oxygen concentration cell was set up using yttria stabilized
zirconia (YSZ) as the electrolyte:
Pt, Ni, NiO | YSZ | Cu-Ni, NiO, Pt
At 1200K, the potential of the cell (electro motive force) was 0.062V, for 30 mol % Ni in
the Cu-Ni alloy. What is the activity of nickel in the alloy? What can you say about the
copper-nickel solid solution?
2. A fuel cell consists of hydrogen/Pt and an oxygen/Pt electrode with both gases at 1
atmosphere. Neglecting ohmic losses and concentration overpotentials, calculate the
power density (W m-2) of the fuel cell at a current density of 100 A m-2, given:
At 298 K, the standard free energy change for the reaction:
H2 (g) + O2 H2O (l)

is

Go = -237,000 J

[The Tafel constant, b for the hydrogen and the oxygen reactions are 0.0295 and 0.09 V
per decade of current density respectively, while the exchange current densities for the
condition in the cells are 10-4 and 10-7 A m-2 respectively; Faradays Constant = 96540 J
mol-1 K-1]

3. In the context of a discharging a battery, distinguish between activation polarisation

and concentration polarisation at a zinc anode plate. Calculate the reversible electrode
potential for pure Zn in contact with an electrolyte with effective concentration of Zn2+ at
0.2M, given the standard electrode potential is -0.76V.
The exchange current density for the above reaction is 0.01 A m-2 and the anodic Tafel
slope b is 0.11V. Calculate the operating electrode potential for a current density of 1 A
m-2.
4. Using Faradays laws, calculate the theoretical capacity in Ah per Kg of pure Li as an
anode in a Li-ion cell. (Molecular wt of Li: 6.94). In practice, for safety reasons, carbon
is used as the anode into which Li can be intercalated up to a maximum of 1 atom of Li
per 6 atoms of C. Calculate the theoretical capacity (Ah) per Kg of the C anode. In the
cathode, 1 Li atom can be intercalated per CoO2 molecule. Calculate the theoretical
capacity (Ah per Kg) of the cathode.
It is found that both the anode and the cathode can practically and safely utilize only 50%
of the available intercalation sites. In a practical Li-ion cell, 20% of weight is accounted

42

for by the electrolyte, separator, current collector, binders and conductive additives in the
cathode. Calculate the capacity of a practical Li-ion cell (i) per Kg of Li and (ii) per Kg
of the cell weight.
The open circuit cell voltage decreases from a maximum initial value of 4.4 V for a fully
charged Li-ion cell [corresponding to LiC6 anode and Li0.5CoO2] to 2.5 V corresponding
to Li0.5C6 anode and LiCoO2] when it is discharged for an average cell potential of 3.5 V.
Calculate the average specific energy density (Wh/Kg) of the cell with respect to 1 Kg of
the cell weight.
Write the anodic, the cathodic and the overall cell reactions during discharge and during
charging.

43