Module 5

Electrochemical energy systems

Batteries and Fuel Cells
 Introduction - Basics
An Electrochemical cell

• An electrochemical cell is a device in which a redox reaction is

utilized to get electrical energy.

• Commonly referred to as voltaic or galvanic cell.

• The electrode where oxidation occurs is called anode while the

electrode where reduction occurs is called cathode.

• Depending upon the changes occurring in the electrochemical cell

these can be of two types namely electrolytic cell and galvanic
or voltaic cell
• Voltages generated by such cells have been referred to as
electromotive force (emf)
 Electrochemical cell (or) galvanic cell
• A device used to convert the chemical energy
produced in a redox reaction to electrical
energy is called an electrochemical cell or
chemical cell.
Ex: Daniel Cell

Red-ox Reactions
Zn (s) Zn 2+ + 2e- (Oxi)
Cu2+ + 2e- Cu (s) (Red)

Ecell = Eo - 2.303(RT/nF) log [Mn+]

Nerns’t equation
 Electrolytic cell

• A device in which the electrical energy is converted to chemical

energy and resulting in a chemical reaction

Refer : Electroplating of
copper or nickel in
chapter II
 Electroplating process

1. CuSO4 Cu2+ + SO42- (At cathode, reduction process)

2. Cu + SO42- CuSO4 + 2e- (At anode, oxidation of metal )

DC battery

Cu
(Anode) Steel object
+ ve Cu2+ (cathode) (-ve)
Cu2+

Cu2+ SO42-
Cu
deposited
surface
 Nominal Voltage

Voltage of a fully charged cell or battery when

delivering rated capacity at a specific discharge rate.

The nominal voltage per cell is 2V for Lead Acid,

1.2V for Nickel-Cadmium, 1.2V for Nickel Metal
Hydride and 3.9V for Lithium Ion (small cells only).
 Operating Voltage
The voltage level by which an electrical
system is designated and to which
certain operating characteristics of
the system are related; also, the
effective (root-mean-square) potential
difference between any two
conductors or between a conductor and
the ground.
 Self Discharge

Self-discharge is a phenomenon in
batteries in which internal chemical reactions
reduce the stored charge of the battery
without any connection between the
electrodes.
Self-discharge decreases the shelf-life
of batteries and causes them to initially have
less than a full charge when actually put to
use.
 Energy Density
Energy density is the amount of energy
stored in a given system or region of space
per unit volume or mass.

Battery Shelf Life

Battery Shelf Life is the time for which

an inactive battery can be stored before it
becomes unusable, usually considered as
having only 80% of its initial capacity.
Capacity of a battery : A battery's capacity
is the amount of electric charge it can deliver
at the rated voltage(nominal voltage) and
expressed in amperes per hour (amp/hr)

Depth of Discharge: DOD is used to describe

how deeply the battery is discharged. If we
say a battery is 100% fully charged, it means
the DOD of this battery is 0%, If we say the
battery have delivered 30% of its energy,
here are 70% energy reserved, we say the
DOD of this battery is 30%..
 Batteries

• Batteries use a chemical reaction to do work on charge and produce

a voltage between their output terminals.

• The basic element in a battery is called an electrochemical cell and

makes use of an oxidation/reduction reaction.

• An electrochemical cell which produces an external current is called

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

• Batteries are devices where several electrochemical systems are

connected together in series.

• And can store chemical energy for later release as electricity

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

 Classification (or) Types of
batteries

Primary battery (Primary cells)

In which the cell reaction is not reversible. When all the
reactants have been converted to product, no more
electricity is produced and the battery is dead.

Secondary battery (secondary cells)

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

Flow battery and fuel cell

In which materials (reactants, products, electrolytes) pass
through the battery continuously,
 Examples for Primary, Secondary and Advanced Primary and
secondary batteries

 Primary batteries
Dry or lachlanche cell
Western-Cd cell, Clark Std Cell
 Advanced Primary batteries
Alkaline battery
Lithium batteries

 Secondary batteries
Lead acid
Nickel-Cadmium

 Advanced secondary batteries

Nickel Metal hydride
Lithium ion or Lithium polymer battery
Zn-Carbon DRY cell (or) LECHLANCHE Cell

Construction of Dry Cell

The venerable carbon-

zinc cell or Lechlanche'
cell was invented in
1866 by Georges
lachlanche and was the
most common small
battery throughout
most of the 20th
century
 The Discharging Reactions of a Dry Cell

Dry cell contains Zn, NH4Cl, ZnCl2 and MnO2

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

Cathodic reaction: 2NH4+(aq) + 2MnO2(s) + 2e- Mn2O3(s) + H2O(l)

+2NH3(aq)
Net Cell Reaction : Zn(s) + 2MnO2 (s) + NH4OH Mn2O3 (S) + H2O(l)+2NH3(aq
)

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

2NH4+(aq) + 2e- 2NH3(g) + H2 (g)

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

ZnCl2 (aq) + 2NH3 (g) Zn(NH3)2Cl2 (sparingly soluble salt)
2MnO2 (s) + H2(g) Mn2O3(s) + H2O(l)
 Applications and disadvantages
• Used in flash lights, transistor radios, calculators etc

• Disadvantages of dry cell

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

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

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

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

declining in application since some of their problems are overcome
in ALKALINE BATTERIES.
 ALKALINE DRY CELLS- Primary Alkaline
Battery

• Alkaline cells overcome some of the problems with Zn-Carbon primary

batteries by using potassium hydroxide in place of ammonium
chloride in the electrolyte.

• Potassium hydroxide is a base or alkaline material, hence the name

"alkaline" batteries. The active materials used are the same as in
the Leclanche cell – zinc and manganese dioxide.
 Construction of Alkaline Battery

Zn powder
 Discharging Chemistry of Alkaline Cell

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

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

• At the cathode: 2MnO2 (s) + H2 O(l) + 2e – → Mn2 O3 (s) +

2OH– (aq)

• Net Cell Reaction : Zn(s) + MnO2(s) + 2H2O(l) → Mn(OH)2(s)

+Zn(OH)2(s)
Advantages and Uses
1. Zinc does not dissolve as readily in alkaline medium
2. Long life maintain it svoltage
3. Used in calculators and watches
4. These cells have much longer shelf life and perform better under drain
and in cold weather.
5. They avoid the use of the zinc-corroding ammonium ions and do not
produce any gaseous products.
 Primary Lithium batteries

Introduction
• One of the main attractions of lithium as an anode material is its
position as the most electronegative metal in the electrochemical
series combined with its low density, thus offering the largest
amount of electrical energy per unit weight among all solid elements.

• Li cannot be used with the traditional aqueous electrolytes due to

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

• In the 1980s progress was made in the use of Li as an anode

material with MnO2, liquid SO2 or thionyl chlorides as the cathode,
and hexaflurophosphate dissolved in propylene carbonate as a
typical organic electrolyte.

• Li cells are generally properly sealed against contact with air and
moisture Whilst the primary lithium battery has been well
established for nearly two decades,
 Primary Lithium Batteries
 Lithium acts as the anode electrode.
 Electrolytes:
o Organic solvents such as tetrahydrofuran, dioxalone,
dimethyl ethane, etc.
o Lithium salts: Lithium perchlorate, lithium tetrafluoro -
borate / - phosphate, etc.
 Lithium in the presence of electrolytes form a very
thin film, which is conductive for Li+ ions
 Battery sizes: Coin cells to Cylindrical cells with high
energy density – energy stored per unit volume
 Cathodes: Solid or Liquid

21
 Types of Li batteries

1. Li Cells with solid cathode 2. Li Cells with liquid cathode

1. Li/MnO2(s) : 3V High energy density, good low-temperature

performance; cost effective. Small in size, low-
Anode
drain applications, Electrical medical devices;
memory circuits
Cathode n Li+ + MnO2 + ne- LinMnO2

2. Li/SO2(l) : 3V High energy density; best low-temperature

performance; long shelf life. High-cost pressurized
system, Military and special industrial needs

2Li + 2SO2 Li2S2O4 ( uses 50% Acrylonitrile (AN) or PC

3. Li/SOCl2(l) : 3.6V High Energy density; long shelf life. Only

low to moderate rate applications. Memory
devices; standby electrical power devices
4Li + 2SOCl2 4LiCl + S +SO2
 Advantages and uses

• Advantages:
High energy density – High current output
Long shelf life
Low self discharge
Less maintenance

• Uses:
Auto focus cameras
Watches
Heart pace makers (Cell: Li/I2 [PVP] , EMF: 2.4-
2.8 V)
 Secondary (or) Rechargeable
Batteries

1. Ni-Cd (NiCad) Battery

2. Lead Acid storage battery

Advanced Secondary (or) Rechargeable Batteries

1. Lithium ion battery

2. Nickel Metal Hydride Battery
 Nickel-Metal Hydride (Ni-MH) Battery
 Active material for Cathode: NiO(OH)
 Active materials for Anode: Metal hydrides such as VH2, ZrH2 and
TiH2 with a hydrogen storage metal alloy (AB5) such as LaNi5
 Choice of Anode materials:
(i) High resistance to chemical oxidation and corrosion
(ii) High electrochemical reactivity
 Electrodes are made of porous nickel foil on which the active
material are coated.
 Electrolyte: KOH (5.35 M)
 Anode and cathode are stacked alternatively in a stainless steel
container and connected in series to get the desired voltage.
 Separator: Polypropylene

25
Cell representation;
MH2 /M// KOH (5.35 M) / NiO(OH)/Ni(OH)2

Reaction occurring during discharge and charging,

Anode: MH2 + 2OH- 2H2O + M + 2e-

Cathode: 2NiO(OH) + 2H2O + 2e- 2Ni(OH)2 + 2OH-

Overall rxn: MH2 + 2NiO(OH) 2Ni(OH)2 + M

Uses:
Cellular phones, Camcorders and Laptop computers

26
Lithium ion batteries

27
 Li+

Li+

LiCoO2 Graphite
Anode materials:
• The anode material is carbon based (lithium carbon intercalation
material

Electrolyte:
• Since lithium reacts violently with water, and the cell voltage is so
high that water would decompose, a non-aqueous electrolyte must
be used.
• A typical electrolyte is LiPF6 dissolved in an ethylene carbonate and
dimethyl carbonate mixture.

Cathode materials:
The most common compounds used for cathode materials are
LiCoO2, LiNiO2 and LiMn2O4.
• Of these, LiCoO2 has the best performance but is very high in cost, is
toxic and has a limited lithium content range over which it is stable.
• LiNiO2 is more stable, however the nickel ions can disorder.
• LiMn2O4 is generally the best value for money, and is also better for
the environment.
29
Discharging

• The following reactions take place upon working

Charging
At the anode: LiC C +xLi+ + xe-
Discharging
Charging
At the cathode: xLi MO2 + xLi++ xe-
LixMO2 Discharging

Charging
30
Overall: LiC +LiMO2 Discharging LixMO2 + C
 Chemistry and Construction
• Anode here is a non-metallic compound, e.g. carbon, which can store
and exchange lithium ions.
• A lithium ion-accepting material (Intercalation), for example CoO2, is
then used as the cathode material, and lithium ions are exchanged back
(deintercalation) and forth between the two during discharging and
charging. These are called intercalation electrodes.
• This type of battery is known as a “rocking chair battery” as the ions
simply “rock” back and forth between the two electrodes.

31
 Lithium-Sulphur Battery
 It is also a rechargeable battery. In this, Li acts as anode.
 The electrons produced from the anode is transferred to S
by a graphite cathode.
 Sulphur accepts the electrons and converts into S2-
 The electrolyte is solid ß–Alumina (NaAl11O17)
 The battery operates at high temperature when Li and S are
in their molten states.

32
Working:

When the anode is connected to cathode through

solid polymer electrolyte, Li+ ions move from
anode to cathode.

The cathode receives lithium ions and electrons

through external circuit that connects both anode
and cathode.

33
At anode (oxidation), the half-cell reaction is,
 
2Li( s )  2Li  2e
At cathode (reduction), the half-cell reaction is,
 2
S( s )  2e  S
The overall cell reaction
nS  Sis,
(s)
2
 (S n 1 ) 2

 2
2Li( s )  S( s )  2Li  S

The element sulphur reacts with S2- ions produced

during the reaction to form the polysulphide ions.

34
 FUEL CELL
 A fuel cell is a device that converts a fuel and air
directly into electricity, heat and water by means of
electrochemical reactions.

 In a fuel cell, the electricity can be generated as

long as the fuel and oxygen are supplied into the
cell.

 It consists of an electrolyte and two electrodes.

 In a fuel cell, the fuel is sent through the anode

and the oxygen is supplied through the cathode.
The electrolyte carries the charged particles from
anode and to cathode and vice versa. 35
 HYDROGEN – OXYGEN FUEL CELL
 The cell consists of two porous carbon electrodes
impregnated with a finely divided platinum or
nickel as catalyst with an electrolyte of 25-40%
KOH.

 Oxygen and hydrogen are fed into the cell under a

pressure of 50 atm.

 The gases and the electrolyte diffuses into the

electrode pores

 The cell develops an emf of 1.23V.

 The efficiency of hydrogen-oxygen fuel cell is 70% .
 The operating temperature is >70 deg C .
 The cell power output is 300 watts to 5 kilowatts
 The cell may be represented as,
C, Pt or Ni / KOH / C, Pt or Ni 36
At anode,
H 2  2 H   2e
2 H   2OH   2 H 2O
____________________
H 2  2OH   2 H 2O  2e
________________________

At cathode,
1/ 2O2  H2O  2e  2OH 

The overall cell reaction is,

H2  1/ 2O2  H2O
37
 Fuel Cells Classifications

1. Low Temperature Fuel Cell (<100 0C):

H2-O2 Fuel Cell, C3H8-O2 Fuel Cell, CH3OH-O2 Fuel Cell

2. Moderate temperature fuel cell (100-300 0C):

H3PO4 (phosphoric acid) Fuel Cell

3. High Temperature Fuel Cells (>500 0C):

Molten Carbonate Fuel Cell, Polymer Electrolyte Fuel Cell

4. Solid Oxide Fuel Cells (>1000 0C)

Limitation:
• Do not store chemical energy
• Constant supply of reactants and removal of products
• Efficiency is higher than conventional power plant
• Free of noise, vibration, heat transfer, thermal pollution etc.,

38
 Solid oxide fuel cells (SOFC)

• Anode, cathode and electrolyte all made up of ceramic

substances
• Anode : porous, to allow the fuel to flow to the electrolyte –
Nickel mixed with ceramic material of the electrolyte

• Cathode: Thin porous layer where oxygen reduction occurs

• Electrolyte : Solid oxide or ceramic electrolyte - Dense layer

of oxygen conducting ceramic. - mixture of ZrO2 and CaO
coated on either side by porous electrode materials. Others
include yttrium stabilized zirconia (YSZ) and gadolinium
doped ceria (GDC)

39
40
• Operate at temperatures as high as1000oC
• Can be configured as rolled tubes or flat plates
• Oxygen ions diffuse through the electrolyte from cathode
and oxidize hydrogen fuel at the anode. This reaction
produces oxygen and electricity

Advantages / Disadvantages
• High efficiency
• Long term stability
• Fuel flexibility
• Low emissions
• High operating temp – longer start up times
• Mechanical / Chemical compatibility issues.

41
 Applications
• Auxiliary power units in vehicles
• Stationary power generation
• By product gases – channeled to turbines to generate more
electricity – cogeneration of heat and power and improves
overall efficiency

42