MTE4599

Materials for energy technologies

So, which technologies ?
Wind turbines and thermal solar power plants; most main
components are made from well-known materials like concrete
and steal. Crucial materials engineering in the wind-turbine blades
made from reinforced polymers please refer to e.g. MTE4572.

Mainly the emerging technologies

*Photo-voltaic cells (power producing solar-cells)
* Materials for water splitting (hydrogen production)
* Materials for storing and converting energy
* Fuel-cell materials

* Need electrochemistry !

Electrochemistry 1.0

Electrode potential
(batteries, fuel-cells and corrosion)

Electrochemical reactions
(water-splitting, dye sensitized solar-cells and reversible batteries)

Electrochemical analytical methods

PART 1

Electrode potential

Electrode potential

Electrode potential

Two equilibriums
Mg2+(aq) + 2e-
Mg
Cu2+(aq) + 2e-
Cu

(Standard) Electrode potential

Equilibrium

E (volts)
-3.03
-2.92
-2.87
-2.71
-2.37
-1.66
-0.76
-0.44
-0.13
0
+0.34
+0.80
+1.50

Standard conditions ? - 1M

(Standard) Electrode potential

Equilibrium

E (volts)
-3.03
-2.92
-2.87
-2.71
-2.37
-1.66
-0.76
-0.44
-0.13
0
+0.34
+0.80
+1.50

Standard conditions ? - 1M

(Standard) Electrode potential

- If you can write the equilibrium equation
Non metals
Cl2 + 2e-
2Cl- (+1.36V)
O2 + 4e- + 4H+
2H2O (+1.23V)
SO42+ + 2e- + 4H+
SO2 + 2H2O (+0.17V)
S + 2e- + 2H+
H2S (+0.14V)
CO2 + 2e- + 2H+
HCOOH (-0.20V)
Carbon (?)

Standard conditions ? - 1M and 1atm

(Standard) Electrode potential

- If you can write the equilibrium equation
Non metals
Cl2 + 2e-
2Cl- (+1.36V)
O2 + 4e- + 4H+
2H2O (+1.23V)
SO42+ + 2e- + 4H+
SO2 + 2H2O (+0.17V)
S + 2e- + 2H+
H2S (+0.14V)
CO2 + 2e- + 2H+
HCOOH (-0.20V)
Carbon (?)

Redox couples
Fe3+ + e-
Fe2+ (+0.77V)
I3- + 3e-
3I- (+0.53V)
Hydroquinone
Etc.

Standard conditions ? - 1M and 1atm

Electrode potential =>

Battery cell

Salt bridge

V
Using standard reduction potentials:
0.34V (- 0.76V) = 1.1V (?)

Standard conditions ?
And if not, call a friend !
A friend called Nernst
The free energy of the electrode reaction:
G = nFE

F = 96,485 C/mol

A friend called Nernst

G = nFE (and G = nFE)

A friend called Nernst

G = nFE (and G = nFE)
And
G = G + RT ln Q

(Q = the reaction quotient)

(http://en.wikipedia.org/wiki/Gibbs_free_energy)

Gives
nFE = nFE + RT ln Q

A friend called Nernst

G = nFE (and G = nFE)
And
G = G + RT ln Q

(Q = the reaction quotient)

Gives
nFE = nFE + RT ln Q
Rearranged it becomes the Nernst Equation:
or
(at 25C)
R = Gas constant = 8.314 J/(K*mol)

F = 96,485 C/mol

Nernst in the lab

What is the electrode potential of Ag+ + e-
Ag at
various concentrations ?
E = 0.80 0.059/1*log(1/[Ag+])
(at 25C)

Nernst in the lab

What is the electrode potential of Ag+ + e-
Ag at
various concentrations ?
E = 0.80 0.059/1*log(1/[Ag+])
E(Ag/Ag+)
1

(at 25C)

0.9
0.8

V vs SHE

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
-10

-8

-6

-4
Log[Ag+]

-2

Nernst in the lab

What is the electrode potential of Ag+ + e-
Ag ?
E = 0.80 0.059/1*log(1/[Ag+])
(at 25C)

Concentration
batteries !
- Any problems in
practical
applications ?

Nernst in the lab

What is the electrode potential of Ag+ + e-
Ag ?
- At different temperatures (1mM solution) ?
E = 0.80 - 8.314*T * ln(1/0.001)
1*96,485

This temperature dependence is the

underlying principle for the thermo-cell
And also the problem of using
reference electrodes at
different temperatures !

Nernst and Water

(at 25C)
Overall:

2H2(g ) + O2(g)

Oxidation:

H2(g) 2H+ + 2e

E = E - (.059/2) log (PH /[H+]2)

E = 0 - (.059/2) 2 pH = 0.059 pH

Reduction:

2H2O

O2(g) + 4H+ + 4e H2O

E = E - (.059/4) log (1/([H+]4 x PO ))

2

And then what ?

E = 1.23 (.059/4) x 4pH =

1.23 0.059 pH

Nernst and Water

(at 25C)

E = 1.23 0.059 pH

E = 0.059 pH

And then what ?

Electrode potential => Fuel cell

A continuous battery

Using standard reduction potentials:

1.23V 0V = 1.23V

Splitting Water
Oxidation H2O O2(g) + 4 H+ + 4e
E = 1.23 0.059 pH

E = 0.059 pH
Reduction: 2H+ + 2e H2(g)

Eh, what just happened ?

We went from measuring potentials on electrodes

to applying potentials to electrodes
much more about that later under

Electrolytic cells and electrolysis

(Next lecture or so)

PART 2

The driving force in science:

What happens when

Applying potential to
a half frog ?
Luigi Galvani, circa 1786,
electrochemistry and
electrophysiology began with
frogs' legs.

Applying potential to an electrode

- in an electrolyte containing ions.
- Just a small potential though !

- + -

Applying potential to an electrode

- in an electrolyte containing ions.
- Just a small potential though !

- + -

+
+
+
+
+

-+ +- +
- + ++ - +
-+ + - +
+
- + +-+

-+-

Double layer capacity

Applying potential to an electrode

- in an electrolyte containing ions.
- Just a small potential though !

Double layer capacity

Surface area
Salt and concentration
Potential (!)
+
+
+
+
+

-+ +- +
- + ++ - +
-+ + - +
+
- + +-+

Characteristic charging/discharging
curve at constant |currents|
V

-+-

+I

-I

Time

Applying potential to an electrode

- in an electrolyte containing ions.
Higher potentials ?

V
?
+
+
+
+
+

-+ +- +
- + ++ - +
-+ + - +
+
- + +-+

+I

-I

-+-

Time

Applying potential to an electrode

- in water containing ions.

+
+
+
+
+

-+ +- +
- + ++ - +
-+ + - +
+
- + +-+

-+-

+I

-I

Time

Applying potential to an electrode

- in water containing ions.

+
+
+
+
+

-+ +- +
- + ++ - +
-+ + - +
+
- + +-+

-+-

-+
+-+
+-+
+++
+ + +

1.23V (?)
Water splitting
Time

Applying potential to an electrode

- in water containing ions,
constant current.
+
+
+
+
+

-+ +- +
- + ++ - +
-+ + - +
+
- + +-+

-+-

-+
+-+
+-+
+++
+ + +

V vs SHE

Oxidation: H2O O2(g) + 4 H+ + 4e

> 1.23V (?)

Water splitting

Reduction: 2H+ + 2e H2(g)

Time

Applying potential to an electrode

(- in water containing ions and ?)

What else could happen ?

ANY reaction where the equilibrium
(standard) electrode potential is within
the potential range where water is stable.

(Oxidative) polymerization
e.g. conducting polymers
Metal deposition:
Mz+ + ze-  M
Metal dissolution:
M  Mz+ + ze-

Gas reactions
e.g. SO2 + 2H2O  SO42+
+ 2e- + 4H+ (+0.17V)

Redox couples e.g.

Ferocene/ferocenium and
Iodine/iodide

Not water ?
- same logic, but different potentials possible

Applying potential to an electrode

Not water ?
- same logic, but different potentials possible
- Electrochemical window

E.g. Propylene carbonate

NB electrolyte salt (ions)
also need to stable !
> 4V

Applying potential to an electrode

How much product are we getting from
electrochemical reactions ?
- Meet our second friend: M. Faraday

Faradays 1st law links the amount (mass/mol) of

material produced with the charge used (Q).
At constant current the number of moles is:

Importance in batteries ?

Applying potential to an electrode

How much product are we getting ?
- Meet our second friend: M. Faraday

Please note that Faradays law is NOT taking the

potential needed to drive the reaction into account
=>
Faradays law can be used to estimate conversion
efficiency (mole per coulomb), but NOT to
evaluate ENERGY efficiency of the reaction.
(Remember: Power = Current x Voltage)

Applying potential to an electrode

- in water containing ions,
constant current.
+
+
+
+
+

-+ +- +
- + ++ - +
-+ + - +
+
- + +-+

-+-

-+
+-+
+-+
+++
+ + +

V vs SHE

Oxidation: H2O O2(g) + 4 H+ + 4e

> 1.23V (?)

Water splitting

Reduction: 2H+ + 2e H2(g)

Time

A closer look;
Equilibrium, over-potential and our next friends
Cu2+ + 2e-
Cu
+0.34 V is the equilibrium potential.
This means that at this potential the reaction:
Cu2+ + 2e-  Cu (cathodic exchange current density ic)
(charge transfer coefficient: c) and
Cu2+ + 2e- Cu (anodic exchange current density ia)
(charge transfer coefficient (symmetry factor): a)

The overall electrode current i is zero,

but the exchange current density i0 is not and
i0 = |ic| = ia at equilibrium
(NB. In one-step, one-electron reactions c + a = 1)

A closer look;
Equilibrium, over-potential and our next friends
Defining the over-potential = E - Eeq

The anodic and catodic exchange currents

can be written as a function of
the exchange current density (io),
the overpotential () and
the symmetry factor ()

ia = io[e(1-)f] and
ic = io[-e(-)f],
where f =nF/RT

We will not go into the

deeper reasoning
behind this math !
The main job for you
is to
accept/agree/imagine
that an exchange
current density exists !

A closer look;
Equilibrium, over-potential and our next friends
Defining the over-potential = E - Eeq

i() = ia + ic = io[ e (1 - ) f e - f ], where f =nF/RT

Known as the Butler-Volmer equation

A closer look;
Overall current depending on exchange current density i0
i = ia + ic = io[ e (1 - ) f e - f ], where f =nF/RT

Here for one-electron process n=1. Also = 0.5

over-potential = E - Eeq

A closer look;
Overall current depending on charge transfer coefficient
i = ia + ic = io[ e (1 - ) f e - f ], where f =nF/RT
Here for one-electron process n=1

Can be 1 ?
At least close
SO2
SO42-

over-potential = E - Eeq

A good electro-catalyst ?
i = ia + ic = io[ e (1 - ) f e - f ], where f =nF/RT
High io for all steps in the reaction
e.g.
O2 + 4e- + 4H+
2H2O
Contains multiple steps
one for each electron transferred + adsorption and desorption

- And no against you

Measuring io and - meet our last friend: Julius Tafel

Take one of the currents in the Butler-Volmer equation

i = ia + ic = io[ e (1 - ) f e - f ], where f =nF/RT

ln i = ln i0 + Fn/RT
Solving for :
c = -b*log i0 + b*log i, (where b is 2.3RT/nF)
This is the Tafel equation

Tafel Slope is 2.3RT/nF

Intercept gives log i0
over-potential = E - Eeq

PART 3

Electrochemical Measurements
Overall two possibilities:
1) Controlling current and measuring potential
2) Controlling potential and measuring current
But we can do it in many different ways depending on what you
want to get out of the measurement
A couple of examples
- Chronovoltammetry (1)
Chronoamperometry (2)
Cyclic Voltametry (CV) (2)

PART 3

Electrochemical Measurements

Test Cell set-up: Two or three electrodes ?

Where the 3rd electrode is a reference electrode
- Chronovoltammetry

- Chronoamperometry - Cyclic Voltametry (CV)

Counter electrode

PART 3

Electrochemical Measurements

Test Cell set-up: Two or three electrodes ?

Where the 3rd electrode is a reference electrode
- Chronovoltammetry

-Chronoamperometry -Cyclic Voltametry (CV)

Counter electrode

Potentiostat
Ref

Working

Counter

PART 3

Electrochemical Measurements

Test Cell set-up: Two or three electrodes ?

Where the 3rd electrode is a reference electrode
- Chronovoltammetry
Potentiostat
Ref

Working

Counter

-Chronoamperometry -Cyclic Voltametry (CV)

PART 3

Electrochemical Measurements

Chronovoltammetry
Applying a constant current and measuring the potential
Typical use:

Battery charge and discharge experiments

Capacitor characterization
Fuel-cell characterization
Metal deposition

PART 3

Electrochemical Measurements

Chronovoltammetry
Applying a constant current and measuring the potential
Typical use:

Battery charge and discharge experiments

Capacitor characterization
Fuel-cell characterization
Metal deposition

PART 3

Electrochemical Measurements

Chronovoltammetry (1)
Applying a constant current and measuring the potential
Typical use:

Battery charge and discharge experiments

Capacitor characterisation
Fuel-cell characterization
Metal deposition

C-rate
1C: charge or discharge in one hour
10C: charge or discharge in six minutes

PART 3

Electrochemical Measurements

Chronovoltammetry
Applying a constant current and measuring the potential
Typical use:

Battery charge and discharge experiments

Capacitor characterization
Fuel-cell characterization
Metal deposition

PART 3

Electrochemical Measurements

Chronoamperometry
Applying a constant voltage and measuring the current
Typical use: Electro-catalytic measurements (over-potential)
Diffusion measurements (e.g. conducting polymers)
Stability test
Electro deposition
0

I (mA/cm )

-0.5

-1.0

Steady state values

(after 1 hour) for
oxygen reduction
on
PEDOT/Au/Goretex
cathode

-1.5

-2.0

-2.5
-600

-400

-200

Ewe (mV vs. SCE)

200

PART 3

Electrochemical Measurements

Cyclic Voltametry (CV)

Applying a potential sweep and measuring the current
Typical use:

Redox activity on electrodes

Diffusion measurements (!)
Determining limiting reaction (surface or bulk)
De-convoluting capacity form resistance and catalysis
Solar-cell characterisation

With rotation disk

Determining reaction (number of electrons involved)

PART 3

Electrochemical Measurements

Sweep- and Cyclic Voltametry (CV)

Applying a potential sweep and measuring the current
Typical use:

Redox activity on electrodes

I
Resistor R
I = 1/R*V

PART 3

Electrochemical Measurements

Sweep- and Cyclic Voltametry (CV)

Applying a potential sweep and measuring the current
Typical use:

Redox activity on electrodes

Capacitor C
Q=CV
I x t =C x V
I = C x V/t

PART 3

Electrochemical Measurements

Sweep- and Cyclic Voltametry (CV)

Applying a potential sweep and measuring the current
Typical use:

Redox activity on electrodes (e.g. Fe2+
Fe3++ e-)

Why this current response ?

PART 3

Electrochemical Measurements

Sweep- and Cyclic Voltametry (CV)

Applying a potential sweep and measuring the current
Typical use:

Redox activity on electrodes

PART 3

Electrochemical Measurements

Sweep- and Cyclic Voltametry (CV)

Applying a potential sweep and measuring the current
Typical use:

Redox activity on electrodes

Why the peak

current ?

Electrochemistry 1.0
This was just the fast introduction !
USE IT in the rest of the course !

Next week: Materials for Fuel-Cells

From last lecture:

Electrode potentials exists !

Applying potential to an electrode

- in acidic water containing ions,
constant current.
V vs SHE

Oxidation: H2O O2(g) + 4 H+ + 4e

How much product are we getting ?

> 1.23V (?)
Water splitting

Reduction: 4H+ + 4e 2H2(g)

Time

Applying potential to an electrode

- in an electrolyte containing ions.
- Just a small potential though !

+
+
+
+
+
+

+
+
+
+
++

Double layer
Using standard reduction potentials:
1.23V 0V = 1.23V