Chapter 15

Electrochemical Engineering

What we will study

Electrochemical principles
Anodes and cathodes
Half cells and simple electrochemical cells

Fuels Cells
Ragone plot and battery capacities

Exploring Engineering

Why electrochemical engineering?

Batteries and fuel cells are deeply embedded in Green
Energy because solar and wind energy systems need to
store electrical energy
Its also a hot topic because some vehicles use batteries
for propulsion such as in hybrid cars and trucks
Electrochemical engineering is the study of what
happens inside batteries, fuel cells and ultracapacitors
So be prepared for a little more chemistry!

Exploring Engineering

Green Energy
Green energy refers to renewable energy supplies
that do not spew forth greenhouse gases nor toxic
impurities
Wind and solar energy are two favored sources
Big disadvantage #1: Only works when the wind blows
or the sun shines
Big disadvantage #2: May make too much electricity
exactly when you dont need it.

Solution: Store the electrical energy until you do need

it.

Exploring Engineering

Load leveling
Electricity not used when
generated, nor available
when needed if the sun or
wind go down
Solution: Battery storage
These may be very
large batteries!
Mismatch of green electric power and use

Exploring Engineering

Solar and Wind Need Equipment!

Batteries
Exploring Engineering

Why Do Batteries Work?

Matter is inherently electrically charged. Simplest
case is ionic bonding (i.e., attraction) in compounds
such as common table salt: Na+Cl- in which Coulombic
forces hold together positively charged sodium ions
and negatively charged chlorine ions. The force
between these ions is:

e2
F= 2
kr

where e is the charge on an electron and r is the

interionic distance. k is the dielectric constant, which
is about 80 for water.
Exploring Engineering

Electrochemistry
When Na+Cl- dissolves in water with k 80, the forces
between ions lessen allowing free ions as Na+ and as
ClIon-containing solutions are called Electrolytes
Overall ion-containing solutions are electrically
neutral
Locally ion-containing solutions have both charged
species at short distances to each other
Batteries use these ions when they can be
separated
Exploring Engineering

Electrolytes, Anodes and Cathodes

Electrodes are classified
as anodes and cathodes
Anodes are sources of
electrons, and cathodes
are sinks for electrons
e- = electrons
E = Electrolyte
C = Cathode
A = Anode

Exploring Engineering

e- flow

+
C

Electrolytes, Anodes and Cathodes

Anodes are sources
of electrons, and
cathodes are sinks
for electrons
e- = electrons

E = Electrolyte
C = Cathode
A = Anode

Exploring Engineering

e- flow
+

C
E

Electrolytes, Anodes and Cathodes

Conventional Current flow

Beware Franklins
error!
e- = electrons
E = Electrolyte
C = Cathode
A = Anode

+
C

Exploring Engineering

Lead-Acid Batteries
These are the batteries you find in a car
Both electrodes are based on lead, Pb one with a
PbO2 coating
The electrolyte is sulfuric acid written H2SO4,
which dissolved in water is 2H+ /SO=4 (the sulfate
ion has two electrons/molecule)
The principle anodic reaction is: Pb Pb++ + 2eThe two electrons flow through the external
circuit to the cathode on which:
PbO2 + 4H+ + SO4= + 2e- = PbSO4 + 2H2O

Exploring Engineering

Lead-Acid Batteries
Product of reaction is PbSO4 which precipitates during
discharge and dissolves during charging.
The anodic voltage at the anode is 0.36V above a
reference cell and the cathodic is 1.69 V below.
Overall cell voltage = ~2.0 V
C

Anodic
0.36 V

Reference
cell
E

Cathodic
1.69V

Exploring Engineering

Can You Power a Car Using Batteries ?

Property
Mass
Energy
Mass energy storage density
Volumetric energy storage
density
Power

Lead-acid
battery
25. kg
3,000 kJ
120 kJ/kg
250 kJ/liter

Gasoline
25. kg
1.2 105 kJ
46,500 kJ/kg
34,400 kJ/liter

5 kW

Typically >100 kW

This battery is too heavy, contains too little energy, and

delivers too little power thats why hybrids are a
popular substitute.
Exploring Engineering

The Electrochemical Series

Cell voltage set by the tendency to transfer
electrons
Half Cell Chemistry
Li+ + e- Li(s)
Na+ + e- Na(s)
Mg++ + 2e- Mg(s)
Zn++ + 2 e- Zn(s)
Fe++ + 2 e- Fe(s)
Ni++ + 2e- Ni(s)
2H+ + 2 e- H2(g)
Cu++ + 2 e- Cu(s)
Cu+ + e- Cu(s)
Ag+ + e- Ag(s)
Pd++ + 2e- Pd(s)

Exploring Engineering

Potential in volts
3.05 V
2.71 V
2.37 V
0.76 V
0.44 V
0.25 V
0.00V (Hydrogen cell is defined as zero)
0.34 V
0.52 V
0.80 V
0.95 V

The Electrochemical Series

These half-cell reactions in principle are
reversible. The more negative the more they
want to lose electrons; the more positive the
more to gain them
This determines how cells will behave

Exploring Engineering

Daniell cell
The electrolytes are
ZnSO4(aq) with a Zn anode
and CuSO4(aq) with a Cu
cathode. Write down the
reactions in each half cell
and explain what happens
in the salt bridge. What is
the voltage?

Exploring Engineering

Daniell cell
In bulk aqueous solution , Zn++ and SO4= must be in
balance with each other.

ZnSO 4 ( Aq ) Zn

++

+ SO

=
4

But the anode is also dissolving and thus yields

some locally extra Zn++ ions according to:

Zn(s) Zn

++

Exploring Engineering

+ 2e

(V =
+0.76V)

Daniell cell
Electrons from the anode flow through the external
circuit precipitating copper at the cathode:

Cu ++ + 2e Cu ( s ) + 0.34V

We have removed copper ions from solution; therefore

there must be a corresponding reduction in SO4= ions
from the electrolyte. They must move into the salt
bridge to exactly counteract the Zn++ ions from the
anodic side.
The cell potential is equal to:

(+0.76 V) + (+0.34 V) = +1.10 V.

Exploring Engineering

Electroplating
An electroplater wants to coat a 10.0 cm by
10.0 cm copper plate with 12.5 micrometers
of silver. How many electrons must pass in
the external circuit? How many coulombs
are passed? If the plating takes 1,200. s
whats the electrical current in amperes in
the external circuit?

Exploring Engineering

Electroplating
Know: Atomic mass of Ag is
108 kg/kmol. Its density is
10,500 kg/m3. Avogadros
number (NAv) is 6.02 1026
atoms/kmol. What we call
current is nothing but the
rate of flow of electrons, so
1.00 A = 1.00 coulomb/s and
one electron carries 1.60
10-19 coulombs.

Exploring Engineering

Conventional
current flow

Electron
flow

Ag

Cu

Ag+, NO3- , H2O

Electroplating
The reaction at the anode is Ag(s) Ag+ + eand the reaction at the cathode is Ag+ + e-
Ag(s); hence one atom of silver dissolves at
the anode and one atom of silver is
deposited at the cathode. For each atom of
silver dissolving at the anode and depositing
at the cathode, one electron must circulate in
the external circuit.

Exploring Engineering

Electroplating
12.510-6 100.10,500
Mass =m
cm4 kg/m [ /
1.0010
= 1.3110-3 kg

] m m

cm

Next convert to kmols:

kmols
1.31 10 3
5
[kg]
=

kmols =
1
.
22
10
kmols

108
kg

Exploring Engineering

Electroplating
Next convert to atoms of Ag(s):
Ag atoms deposited =
5

1.22 10 6.02 10

26

= 7.32 10 21[kg ][atoms / kg ]

= 7.32 10 atoms
21

Exploring Engineering

Electroplating
Next convert to mass of Ag(s):

7.32 10 21 1.6010 19 [e ][coulombs/e- ]

= 1.17 10 coulombs
3

1.17 10
Hence current =
[C/s] = 0.975A
1200.
3

Exploring Engineering

Fuel Cells
Fuel cells are just continuously refueled batteries.
They will not discharge while electrochemical
fuel is being fed to them.
Most fuel cells depend on Proton Exchange
Membrane or PEM to catalyze electrode
reactions

2 H 2 4 H + + 4e Anodic Rxn
+

4 H + 4e + O2 2 H + 2OH 2 H 2 0
Cathodic Rxn
Exploring Engineering

Fuel Cells

http://aq48.dnraq.state.ia.us/prairie/images/fuelcell.jpg

Exploring Engineering

Fuels cells
Note: Only H2 and O2(i.e.,air) in and only H2O
out.
Cell voltage is 1.23 V for overall
rxn H2 + O2 = H2O
Apparently no green house gas pollution!
Unfortunately to make H2 needs copious CO2

Exploring Engineering

The Ragone Chart

Batteries must supply both energy and power
Typically batteries supply current measured at mA/cm2 of
electrode area at a few volts
The more electrode area, the greater the current; this may
be internal area packing or simply more cells placed in
parallel
The more cells in series the higher the voltage

But its the application that demands whether the cell

can deliver both enough energy (say mileage between
charges on an electric car) and power (say to pass
another car)

Exploring Engineering

The Ragone Chart

The best measures of energy and power efficiency are
their mass densities: e = E/Wt (Whr/kg) and p = P/Wt
(W/kg)
The energy density delivered by a power source for a
time t is simply e = p t.
Take log base 10 of this equation:
log10 e = log10 p + log10 t

Plot the log10 energy density of a battery vs. log10

power density for the same battery and you get
the Ragone Plot

Exploring Engineering

The Ragone Chart

Modified from a graphic of Maxwell Technologies: http://www.maxwell.com.

Exploring Engineering

The Ragone Chart

Very convenient way to compare different
electrochemical sources
Ideally you want to have your cake and eat it by
being in the upper right corner
Reality shows what can be achieved by competing
electrochemical sources
Ultracapacitors are storage devices that can
store thousands of times the energy capability
of an electrical capacitor.

Exploring Engineering

Ragone Chart
rs
u
o
0h

1
100

Energy, Whr/kg

That that the form of

log10 e = log10 p + log10
t is y = mx + c and has a
slope of m =1 given
the log10 scaling in
chart.
The batterys discharge
time is given by e/p

1,000

ou
h
1

360

10

36

0.1

3.6

6
0.3

m
36

0.01

10

100
Power, W/kg

Exploring Engineering

1,000

10,000

Summary
Green energy and load storage and leveling
Electrochemical series
Simple electrical cells
Simple electrochemistry

Principles of fuel cells

Ragone chart to characterize

Exploring Engineering