MJ2411 RENEWABLE ENERGY TECHNOLOGY

MODULE: Electrochemical Systems for Energy

Introduction to electrochemical cells
Part 1.1
Prof. Massimo Santarelli
General Outline

Notes on electrochemical cells:

•general principles
•thermodynamics
•polarization
Exampe: Fuel Cell (PEMFC stack)
Exampe: Fuel Cell (SOFC complete system)
 MJ2411 RENEWABLE ENERGY TECHNOLOGY

MODULE: Electrochemical Systems for Energy

Introduction to electrochemical cells
Part 1.2
Prof. Massimo Santarelli
 Energy pathways: thermal engines
vs electrochemical generators
Chemical Energy

COMBUSTION

High T Heat
ELECTRO-
Thermodynamic CHEMICAL
Cycle GENERATOR
(FUEL CELL)
Mechanical Energy

Electrical
Generator

Electrical Energy
 Electrochemical cells: general

DV

ANODE ELECTROLYTE CATHODE

ELECTRODE LAYER ELECTRODE

IONIC
OXIDATION CONDUCTION REDUCTION

GLOBAL REACTION: REDOX REACTION

 Electrochemical cells
Energy Producer: chemical energy → electric energy
(galvanic cell, fuel cell)

e-

ANODE CATHIONIC CATHODE

ELECTRODE ELECTROLYTE ELECTRODE
(e.g. Nafion)
OXIDATION REDUCTION

- H+

+
H2 → 2H+ + 2e- Example ½O2 + 2H+ + 2e- → H2O

REDOX REACTION H2 + ½O2 → H2O

 Electrochemical cells
Energy Producer: chemical energy → electric energy
(galvanic cell, fuel cell)
e-

ANODE ANIONIC CATHODE

ELECTRODE ELECTROLYTE ELECTRODE
(e.g. Y2O3)
OXIDATION REDUCTION

- O2-

+
H2 + O2- → H2O + 2e- Example ½O2 + 2e- → O2-
REDOX REACTION H2 + ½O2 → H2O
 Electrochemical cells
Energy Consumer: electric energy → chemical energy
(electrolytic cell)
e-

ANODE CATHIONIC CATHODE

ELECTRODE ELECTROLYTE ELECTRODE
(e.g. Nafion)
OXIDATION REDUCTION

+ H+
-
H2O → 2H+ + ½O2 + 2e- Example 2H+ + 2e- → H2

REDOX REACTION H2O → H2 + ½O2

 Electrochemical cells
Energy Consumer: electric energy → chemical energy
(electrolytic cell)
e-

ANODE ANIONIC CATHODE

ELECTRODE ELECTROLYTE ELECTRODE
(e.g. KOH or NaOH)
OXIDATION REDUCTION

+ OH-
-
2OH- → ½O2 + H2O + 2e- Example 2H2O + 2e- → H2 + 2OH-

REDOX REACTION H2O → H2 + ½O2

 MJ2411 RENEWABLE ENERGY TECHNOLOGY

MODULE: Electrochemical Systems for Energy

Introduction to electrochemical cells
Part 1.3
Prof. Massimo Santarelli
Electrochemical cell
Faraday’s Law
The relationship between charge passed and
amount of a substance oxidized or reduced at
an electrode is linked to two statements:
1. The amount of reacting substance [mol/s] is directly
proportional to the charge passed

I  mol 
ni 
zi  F  s 
2. For a specified amount of charge passed, the masses of
reacting substances [kg/s] are proportional to their
molar mass
I  kg 
Gi  Mi  
zi  F  s 
Electrochemical cell
Ionic conduction
The current flow in an electrolyte results from the movement
of positive and negative ions. Ion motion is caused by
potential (mainly) and concentration gradients.
Considering especially the potential gradient, the behavior of
ionic conductors is as follows:

 ionic, j  F  z  u j  c j   m
2 2
j
1

where
F: Faraday constant 96487 [C/mol]
z: charge number
u: ionic mobility [m2/sV] = [m/s]/[V/m]
c: concentration [mol/m3]
 Electrochemical cell
Ionic conduction
Considering especially the potential gradient, the behavior of
ionic conductors compared to electronic conductors is as
follows:

 ionic
 ionic  1   m 1
T
0

 electronic  107   m1  electronic

0
T
1  ionic  1  electronic 
 10   
 ionic T   electronic T 
 Electrochemical cell
Thermodynamics
Applying the first and the second law to a cell, in the hypothesis that the
reaction is thermodynamically reversible, the result is

  Wer  nP  h P (T , p)  nF  h F (T , p)  nox  hox (T , p)  0


 nP  s P (T , p)  nF  s F (T , p)  nox  s ox (T , p)  0
T
Dividing each term by the molar mass flow of the fuel, the result is
r nP n
q  le   h P (T , p)  1  h F (T , p)  ox  hox (T , p)  0
r
nF nF
q  l e  P  h P (T , p)  1  h F (T , p)   ox  hox (T , p)  0
q nP nox
  s P (T , p)  1  s F (T , p)   s ox (T , p)  0
T nF nF
q
 P  s P (T , p)  1  s F (T , p)   ox  s ox (T , p)  0
T
q
 D s react (T , p)  0
r
q  l  D h react (T , p )  0
e
T
 Electrochemical cell
Thermodynamics
The internal chemical work
r
 
l   Dhreact (T , p)  T  D s react (T , p)  D g react (T , p)
e

The external electrical work

r Wer I  E
l 
e   zFE
n F I
zF
And finally the well known Nernst equation that define the open circuit voltage
for a reversible cell
D g react (T , p)
z  F  E  D g react (T , p) E
zF
 Electrochemical cell
Thermodynamics
The Nernst equation (open circuit voltage) can be developed in
this expression:

D g react T , p0  R  T  FUEL
p 

E   ln FUEL
zF zF  PRODUCT
p 

PRODUCT

where p0 is a reference pressure (usually ambient pressure)

and pFUEL and pPRODUCT are the partial pressure of FUEL and
PRODUCT chemical species in the complete redox reaction
 Electrochemical cell
Thermodynamics On the cathode
On the anode
1
 H 2  2H  2e  
O2  2e   O2
  2
2
  H 2O
complete cell
 2H O
1
CO  CO2  2e  H 2  O 2  H 2O
2
 2 2
 CO  O  CO 2 1
H 2O
CO+ O2  CO2
2
2H+ O2
H2 2- H2 Oxid. CO Oxid.
O
CO2 Dg0 , kJ/kmol 228.62 257.14
Dh0 , kJ/kmol 241.95 283.20
Ds0 , kJ/  kmol  K  44.44 86.88
CO Anode Electrolyte Cathode
 MJ2411 RENEWABLE ENERGY TECHNOLOGY

MODULE: Electrochemical Systems for Energy

Introduction to electrochemical cells
Part 1.4
Prof. Massimo Santarelli
Electrochemical cell
Polarization
 Electrochemical cell
Polarization

V (i)  E act (i) ohm(i) diff (i)

Overvoltage type and Equation
related phenomena

1  i 
Activation Overvoltage
R T
(charge transfer on the  act   sinh  
electrode)  F  2  i0 
Ohmic Overvoltage t
(charge conduction on
ohm  R  I     I 
electrodes and
S
electrolyte) t
  i  S   t i  r i
S
Diffusion Overvoltage
(mass transport in the R T  i 
electrode) diff   ln 1  
zF  il 
 Electrochemical cell
Polarization

i0: is the exchange current

density of the electrode
[A/m2], function of
temperature, electrode
material, catalyst (type,
quantity, granulometry).
In synthesis, it is a
function of the length of
the three phase boundary
(TPB)
 Electrochemical cell
Polarization

r: is the area specific

resistance [ m2],
function of temperature,
material of electrode
and electrolyte (type,
granulometry),
conduction path of the
charged species.
 Electrochemical cell
Polarization
il: is the limit current density [A/m2], function of
the diffusion capability of the reactant molecular
species inside the electrode:

z  F  D c j
eff
j
il , j 
t
where
Deff: effective diffusivity of species j
[m2/s], function of temperature, layer
porosity and tortuosity
c∞: concentration [mol/m3] of the species
J in the distribution channel
t: thickness [m] of the transport layer
 Electrochemical cell
Heat
A electrochemical cell exchanges heat during operation. The
contribution are:
Entropy change of reaction: the sign depends on the direction of
reaction (heat released for galvanic cells, heat consumed for
electrolytic cells)
I
 react  T  D s  n  T  D s 
zF
Irreversibilities, due to overpotentials (e.g. Joule heating for ohmic
effect):
irr  I   j i 
j
 Electrochemical cell
Heat
The complete expression of heat exchanged
during operation is as follows:

é -Dhreact (T) ù
F = Freact + Firr = I × ê -Vc (i)ú
ë z× F û
where

Dhreact : molar enthalpy of reaction [J/mol]