Electrochemical energy systems

Batteries and Fuel cells

Unit V:
Electrochemical energy systems: Basic concepts of
electrochemistry and electrochemical energy systems.
Conventional primary batteries: Dry cell. Advanced primary
batteries: Lithium and alkaline primary batteries. Conventional
secondary batteries: Lead-acid, nickel-cadmium secondary
batteries. Advanced secondary batteries: Nickel-Metal hydride and
lithium-ion secondary batteries. Fuel cells: Key issues Hydrogen-
oxygen fuel cells new generation fuel cells electric vehicle
application solid oxide fuel cells.
Electrochemistry
Electrochemistry - study of the relationships which exist
between the flow of electrons and chemical reactions
Types of electrochemical systems
electrolytic - chemical reaction which occurs when
electrical current is passed through solution
voltaic/galvanic - spontaneous reactions able to
generate a supply of electricity (e.g., batteries)
Spontaneous redox reactions are coupled in such a way
(i.e., an electrochemical cell) as to allow electrons to flow
through an external circuit
The electrochemical cell design: half-cells (2); salt bridge;
potentiometer; electrodes; electrolyte solutions;
conducting wire
2
Electrochemistry
A complete redox reaction takes place in a galvanic cell
Overall reaction separated into half-reactions which take
place at the anode and cathode
Given the following reaction:
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)
the two half-reactions are:
oxidation half-reaction: Zn(s) Zn
2+
(aq) + 2e
-
(anode)
reduction half-reaction: Cu
2+
(aq) + 2e
-
Cu(s)
(cathode)
Electrode reactions:
Anode: site of oxidation; electrons originate there; neg.
pole of cell (anions migrate toward)
Cathode: site of reduction; electrons consumed there;
pos. pole of cell (cations migrate toward)
3
Two electrodes are connected by an external circuit
4
Daniel Cell Design
Cell Notation
Cell notation is used to describe structure of galvanic cell
For the Zn/Cu cell, the galvanic cell notation is:

Zn(s) Zn
2+
(aq) Cu
2+
(aq) Cu(s)

= phase boundary
= salt bridge
anode reaction: to the left of the salt bridge
cathode reaction: to the right of the salt bridge
both half-cell reactions in order of spontaneous reaction
Zinc solid reacts to form zinc(II) ion at the anode
Copper(II) ion reacts to form copper metal at the cathode
5
Electromotive Force
Electrons are driven (pushed) through conducting wire
in the direction of anode cathode by cell force
Origin of cell force is maximum electric potential
difference between electrodes or electromotive force
(E
cell
) or cell potential
Potential difference - difference in electrical potential
(electrical pressure) between two electrodes; standard
unit of cell potential difference is the Volt
Electrical work
electrical work = charge moved X potential
difference
J = C X V
w
max
= G = -nFE
cell
6
Standard Cell Potentials
Standard potential of galvanic cell = sum of standard
half-cell potentials of ox at anode and red at cathode
E
o
cell
= E
o
ox(anode)
+ E
o
red(cathode)

Since -E
o
red
(anode) = E
o
ox
(anode)
E
o
cell
= E
o
red(cathode)
- E
o
red(anode)

For a spontaneous cell reaction, E
o
cell
is positive (since
Gibbs free energy change must be < 0)
Method developed to estimate standard cell potentials
under standard conditions (1 atm, 1 M, 25
o
C)
Standard cell potentials termed standard reduction
potentials according to above formula
SHE used to determine standard reduction potentials
7

8
Electrode
Electrically conductive
Can be inert electrode or reactive
Charge transfer takes place at the interface
Ion intercalation electrode used in secondary Li-
ion batteries
Every electrode has its electrode potential,
depends on the material and the electrolyte
which is contact

Electrode
Anode (positive terminal), Cathode (negative
terminal) in electrolytic cell
Anode ( negative ), Cathode ( positive ) in
Galvanic cell
Three electrode system for electrolytic cell

Electrolyte
Ionically conductive medium
Electronically insulating
Can solid, semisolid,(gel), liquid
Should have high ionic conductivities
The solvent should have high potential window,
specially organic electrolytes have high potential
window ( in Li-ion batteries)
In this potential window electrolytes are inert
under the electrochemical conditions
Slide
12 of
52
E
cell
, G, and K
eq

Cells do electrical work.
Moving electric charge.
Faraday constant, F = 96,485 C mol
-1

elec
= -nFE
G = -nFE
G = -nFE
Slide
13 of
52
Spontaneous Change
G < 0 for spontaneous change.
Therefore E
cell
> 0 because G
cell
= -nFE
cell

E
cell
> 0
Reaction proceeds spontaneously as written.
E
cell
= 0
Reaction is at equilibrium.
E
cell
< 0
Reaction proceeds in the reverse direction
spontaneously.
Relationship Between E
cell
and K
eq

G = -RT ln K
eq
= -nFE
cell
E
cell
=
nF
RT
ln K
eq

Slide
15 of
52
E
cell
as a Function of Concentration
G = G -RT ln Q

-nFE
cell
= -nFE
cell
-RT ln Q
E
cell
= E
cell
- ln Q
nF
RT
Convert to log
10
and calculate constants
E
cell
= E
cell
- log Q
n
0.0592 V
The Nernst Equation:
Galvanic cell
Electrolytic cell
HISTORY OF BATTERIES
1800 Voltaic pile: silver zinc
1836 Daniell cell: copper zinc
1859 rechargeable lead-acid cell
1868 Leclanch: carbon zinc wet cell
1888 Gassner: carbon zinc dry cell
1899 Junger: nickel cadmium cell
1946 Neumann: sealed NiCd
1960s Alkaline, rechargeable NiCd
1970s Lithium, sealed lead acid
1990 Nickel metal hydride (NiMH)
1991 Lithium ion
1992 Rechargeable alkaline
1999 Lithium ion polymer
HISTORY OF BATTERIES
Battery :-
A battery is a storage device used for the storage of chemical
energy and for the transformation of chemical energy into electrical
energy
Battery consists of group of two or more electric cells connected
together electrically in series.
Battery acts as a portable source of electrical energy.
Energy produced by an electrochemical cell is not suitable for
commercial purposes since they use salt bridge which produce internal
resistance which results in drop in the voltage. The drop in voltage is
negligible only for a small interval of time during which it is being used.
Batteries are of 3 types. Namely
Primary Batteries (or) Primary Cells
Secondary Batteries (or) Secondary Cells
Reserve Batteries
Fuel Cells (or) Flow Batteries

Primary (Disposable) Batteries
Leclanch Cells (zinc carbon or dry cell)
Alkaline Cells
Mercury Oxide Cells
Zinc/MnO
2
Cells
Aluminum / Air Cells
Lithium Cells
Liquid cathode lithium cells
Solid cathode lithium cells
Solid electrolyte lithium cells
Secondary (Rechargeable) Batteries
Leadacid Cells
Nickel/Cadmium Cells
Nickel/Metal Hydride (NiMH) Cells
Lithium Ion Cells


Daniel cell primary batteries
Anode
Zn Zn
2+

Cathode
Cu
2+
+ 2e
-
Cu

Cell reaction
Zn + cu
2+
+ SO
4-
ZnSO
4
+ Cu

EMF 1.1 V
The Leclanch (Dry) Cell
Slide
24 of
52
(Zn/MnO
2
+ C) Leclanch cell
Cathode
2MnO
2
+ 2H
2
O + 2e
-
2MnO(OH) + 2OH
-


Anode
Zn Zn
2+
+ 2e
-

Secondary reaction
NH
4
Cl + 2OH
-
NH
3
+ 2Cl
-
+ 2H
2
O
Zn
2+
+ NH
3
+ 2Cl
-
[Zn(NH
3
)
2
] Cl
2

MnO
2
+ C cathode was dipped into 20% NH
4
Cl
In dry cell - Electrolyte in form of paste is used


Advantages:
1) These cells have voltage ranging from 1.25v to 1.50v.
2) Primary cells are used in the torches, radios, transistors,
hearing aids, pacemakers, watches etc.
3) Price is low.


Disadvantages:
These cells does not have a long life, because the acidic
NH
4
Cl corrodes the container even when the cell is not in
use.
Alkaline Dry Cell
Zn/MnO
2
with KOH as electrolyte
Anode : Zn + 2OH
-
ZnO + H
2
O + 2e
-
Cathode
2MnO
2
+ 2H
2
O + 2e
-
2MnO(OH) +2OH
-

Alkaline cells have high output
capacity and current carrying ability
Less variation in output capacity
Zn electrodes must be very pure to
avoid hydrogen evolution reaction
The Silver-Zinc Cell: A Button Battery
Zn(s),ZnO(s)|KOH(satd)|Ag
2
O(s),Ag(s)
Zn(s) + Ag
2
O(s) ZnO(s) + 2 Ag(s) E
cell
= 1.8 V
Lithium primary batteries
Li/ Ethylene carbonate + Propylene carbonate+
Li
+
/MnO
2 .
Li/ Ethylene carbonate + Propylene carbonate+
Li
+
/organic sulphides
Li/ SOCl
2 ,
Li/ electrolyte/SO
2 ,
Li/ Electrolyte/I
2
+
polyvinyl pyridine



Anode
Li Li
+
+ e
-

Cathode
MnO
2
+

xLi
+
+ xe
-
Li
x
MnO
2


Give high energy density
Li metal have high capacity
Passive layer formation on anode
Lead-acid battery
Electrolyte 20 % H
2
SO
4

H
2
SO
4
Concentration decreases
with discharging and regained on
charging

This can tested by specific gravity
measurement of H
2
SO
4

Cell voltage 1.88 2.15 V
PbO
2
+ Pb + H
2
SO
4
2PbSO
4
+ 2H
2
O
discharging
charging
Basics-Cell Chemistry
At the positive plate:
PbO
2
+ 4H
+
+ SO
4
2-
+ 2e
-
PbSO
4
+ 2H
2
O

At the negative plate: Pb + SO
4
2-
PbSO
4
+ 2e
-



Total Cell Reaction: PbO
2
+ Pb +2H
2
SO
4
2PbSO
4
+2H
2
O

Note: Active materials include lead dioxide, lead and sulfuric
acid.


D
C
D
C
D
C
There are four stages in the
dischargingcharging cycle:

Fully Charged
Discharging
Fully Discharged
Charging

Positive plate covered with lead oxide
(PbO2)
Negative plate covered with a
sponge lead (Pb)
Electrolyte contains water (H2O)
and a sulfuric acid (H2SO4)
FULLY CHARGED
Current flows in the cell from the negative
to the positive plates.
Electrolyte separates into hydrogen (H2)
and sulfate (SO4).
The free sulfate combines with the lead
(both lead oxide and sponge lead)
and becomes lead sulfate (PbSO
4
).
The free hydrogen and oxygen
combine to form more water,
diluting the electrolyte.

DISCHARGING
Both plates are fully sulfated.
Electrolyte is diluted
to mostly water.

DISCHARGED
Reverses the chemical reaction
that took place during discharging.
Sulfate (SO
4
) leaves the positive
and negative plates and combines
with hydrogen (H2) to become
sulfuric acid (H2SO4).
Hydrogen bubbles form at the
negative plates; oxygen appears
at the positive plates.
Free oxygen (O2) combines with
lead (Pb) at the positive plate to become
lead oxide (PbO2).
CHARGING
Ni-Cd battery
Cd / CdO / KOH / NiO or Ni
2
O
3
/
Ni

Other systems with Fe/FeO,

These batteries comes in a
discharged state

Cell voltage 1.3 V

Nickel Cadmium (Ni-Cd)
1.2V, 400 Cycles
Inexpensive Simple charging
low energy density Memory effect
high self discharge (20% month)
Toxic
Advantages and uses
1. The Nickel-Cadmium cell has small size and high rate
charge/discharge capacity, which makes it very useful.
2. It has also very low internal resistance and wide
temperature range (up to 70C).
3. It produces a potential about 1.4 volt and has longer life
than lead storage cell.
4. These cells are used in electronic calculators, electronic
flash units, transistors etc.
5. Ni- Cd cells are widely used in medical instrumentation
and in emergency lighting, toys etc.


Ni Metal hydride batteries
Alloy electrodes - anodes
AB
2
, A - Group IV metal (Ti),
B Group VIII (Ni)
AB
5
, A - Lanthanum (La),
B Group VIII (Ni)
These alloys help in better
M-hydrides formation
This have better performance
than Ni- Hydrogen batteries
Cell voltage = 1.35 V




Anode :
MH+2OH
-
M+H
2
O + 2e
-

Cathode :
NiO(OH)+H
2
O+e
-
Ni(OH)2+OH
-


Over all reaction :
MH+ NiO(OH) M + Ni(OH)2
Chemistry:
LaNi
5
, TiMn
2
, ZrMn
2
(-), nickel hydroxide (+)
Potassium hydroxide aqueous electrolyte
Features:
Higher energy density (40%) than NiCd
Nontoxic
Reduced life, discharge rate (0.2-0.5C)
More expensive (20%) than NiCd
reduced memory effect Less-toxic









D
C
D
C
D
C
Li-ion Battery

+
-
e
-
e
-
e
-
e
-
Li
+
conducting electrolyte

LiCoO
2
Li
x
C
6
Graphite

charge

discharge

Li
+
Li
+
Electrode redox reactions on charge:
Cathode oxidation : LiCoO
2
Li
1-x
CoO
2
+ xLi
+
+ xe
-
Anode reduction : xLi
+
+ xe
-
+ C
6
LiC
6

discharge is the opposite

Fuel cells
PEM fuel cell
Parts of a Fuel Cell
Anode
Negative post of the fuel cell.
Conducts the electrons that are freed from the hydrogen molecules so that
they can be used in an external circuit.
Etched channels disperse hydrogen gas over the surface of catalyst.
Cathode
Positive post of the fuel cell
Etched channels distribute oxygen to the surface of the catalyst.
Conducts electrons back from the external circuit to the catalyst
Recombine with the hydrogen ions and oxygen to form water.
Electrolyte
Proton exchange membrane.
Specially treated material, only conducts positively charged ions.
Membrane blocks electrons.
Catalyst
Special material that facilitates reaction of oxygen and hydrogen
Usually platinum powder very thinly coated onto carbon paper or cloth.
Rough & porous maximizes surface area exposed to hydrogen or oxygen
The platinum-coated side of the catalyst faces the PEM.
Types of Fuel Cells
- Transportation applications
- Space application
- avoids the need of pure H
2
- envisaged for
stationary power
plants
- high volumetric energy
density
Anode Cathode
H
2
-O
2
fuel cell(Alkaline Fuel Cell)
H
2
O
2
H
+
Overall: H
2
+ O
2
H
2
O
O
2
+ 2H
+
+ 2e
-
H
2
O H
2
2H
+
+ 2e
-
Electrolyte
e
-
H
2
-O
2
fuel cell
O
2
(g) + 2 H
2
O(l) + 4 e
-
4 OH
-
(aq)
2{H
2
(g) + 2 OH
-
(aq) 2 H
2
O(l) + 2 e
-
}
2H
2
(g) + O
2
(g)

2 H
2
O(l)

E
cell
= E
O
2
/OH
- - E
H
2
O/H
2


= 0.401 V (-0.828 V) = 1.229 V
Electrodes
Need of porous electrode substrate
Need of electro catalysts
Noble metal electro catalysts shows high
performance
Stability of electro catalysts under the given
experimental conditions
Good electrical conductivity of these electrodes
Electrolyte in fuel cell
Alkaline electrolyte ( 85 % KOH)
Phosphoric acid electrolyte
Solid polymer electrolyte conducting protons
proton exchange membranes ( Nafion)
Recent studies on anion exchange membranes
Fuel cell electrode reactions
Direct methanol fuel cell
Solid oxide fuel cell
High temperature fuel cell
Oxide ion conductor as electrolyte

Solid oxide fuel cell
Electrolyte - fused mixture of
Yttrium dioxide + Zirconium
dioxide
Cells operate 800 1000
o
C
Charge transfer by O
2-
ions
Electrode materials should have
good oxide ion diffusion coefficient
Cathode -LaMnO
3
, Anode
Ni/ZrO
2

No need for noble metal catalysts,
no corrosion problem as
in case of liquid electrolyte systems
H
2
+ CO (reformate gas), CH
4
can
be used at anode


Advantages/Disadvantages of Fuel
Cells
Advantages
Water is the only discharge (pure H
2
)
Disadvantages
CO
2
discharged with methanol reform
Little more efficient than alternatives
Technology currently expensive
Many design issues still in progress
Hydrogen often created using dirty energy (e.g.,
coal)
Pure hydrogen is difficult to handle
Refilling stations, storage tanks,
Other energy resources
Solar cells
Tidal power generation
Nuclear power
Geothermal energy
GENERAL APPLICATIONS
Emergency power - Lithium cells, water
activated batteries
Standby power - Lead acid
Medical implants , long life, low self discharge,
high reliability - Lithium primary, button and
special cells
Cordless equipment - NiCad, Lithium Ion
Hearing aids, watches, calculators, memory back
up, wireless peripherals: Button and coin cells,
Zinc air, Silver oxide.

Distinction between Primary, Secondary & Fuel cells
Primary Secondary Fuel cells
1) It only acts as galvanic
or voltaic cell. i.e.,
produces electricity
1) It acts as galvanic or
voltaic cell while
discharging (produces
electricity) and acts as
electrolytic cell (consumes
electricity)
1) It is a simple galvanic or
voltaic cell. i.e., produces
electricity

2) Cell reaction is not
reversible.
2) Cell reaction is
reversible.
2) Cell reaction is
reversible.
3) Cant be recharged. 3) Can be recharged 3) Energy can be
withdrawn continuously
4) Can be used as long
as the active materials
are present
4) Can be used again and
again by recharging.
4) Reactants should be
replenished continuously. it
does not store energy.
eg: Leclanche cell or Dry
cell, Lithium cell.
eg: Lead storage battery, Ni-
Cd battery, Lithium ion cell
eg: H
2
&O
2
Fuel cell
CH
3
OH &O
2
Fuel cell
Uses: In Pace makers
watches, Transistors, radios
ect.
Uses: In electronic
equipments, automobile
equipments, digital cameras,
laptops, flash light.
Uses: Great use in space
vehicles due to its light weight
(product of is source of fresh
water for astronauts )
Reference :
Engineering Chemistry R.P.Mani,K.N.Mishra,B.RamaDevi,Cengage learning
publications,New Delhi(2009).

Engineering Chemistry by P.C.Jain & M.Jain, Dhanpatrai & Co., New Delhi
(2005).
Modern Aspects of Electrochemistry, J. OM. Bockris and A. K. N. Reddy,
Kluwer Academic, 2000.
Electrochemistry, Prof. B. Viswanathan et al., S.Viswanathan Publishers, 2007
Electrochemistry of Semiconductors, Adrian W. Bott, Current Separations 17
(1998) 87 91.
Electrochemical capacitors, Brian E. Conway,
http://electrochem.cwru.edu/ed/encycl