10-06-2023

Electrochemical Materials Science

Supercapacitors

Capacitor

1
 10-06-2023

Impedance Spectroscopy
The ac analogue of Ohm’s law Z* = Z - jZ
j = -1

2
 10-06-2023

Impedance Spectroscopy

The apex of the semicircle obeys

the Maxwell relationship:

1 = maxRC

The time corresponding to one cycle

of frequency, max, is occasionally
termed the time constant of the arc

P. Simon, Y. Gogotsi, Nature Mater. 7 (2008) 845.

3
 10-06-2023

Why Electrochemical Capacitors?

Energy storage – batteries & capacitors

Li-ion batteries – slow power delivery & uptake
Electrochemical Capacitors (ECs) – emerging energy storage technology
Electrochemical double layer capacitors (EDLCs) & pseudocapacitors
EDLCs – emergency doors of Airbus A380
Portable electronics to hybrid electric vehicles
Developing new materials & understanding electrochemical interface at
nanoscale - important

Why Electrochemical Capacitors?

J. R. Miller, A. F. Burke, Electrochem. Soc. Interface 17 (2008) 53.

4
 10-06-2023

Batteries vs. Electrochemical Capacitors

J. R. Miller, P. Simon, Electrochem. Soc. Interface 17 (2008) 31.

Batteries vs. Electrochemical Capacitors

A. K. Shukla, S. Sampath, [Link], Curr. Sci. 79 (2000) 1656.

5
 10-06-2023

Electrochemical Capacitor
• Storing electrical charge on surface
• Storing static electricity between two electrodes
• Eg. Leiden jar
• Glass jar with conducting metal foil coating the
inner and outer surface
• Glass – dielectric medium
• Discovered by Ewald Georg von Kleist (German)
and Pieter van Musschenbroek (Dutch, Leiden) –
1745-’46
• Capacitor
• Capacitance – capability for charge storage per volt
– C - Farad
• Capacity in battery – extent of Faradaic charge
storage – coulombs or watt-hour

Electrochemical Capacitor

P. Jampani, A. Manivannan, P. Kumta, Electrochem. Soc. Interface 19 (2010) 57.

6
 10-06-2023

Electrochemical Capacitor

At voltage difference V between two plates with charges +q

and –q,
stored energy, G = ½ CV2
where G is Gibbs free energy which increases with square of V

First patent in 1957 by Becker - the principle of charge

storage was first used in electrical energy storage in a cell or
battery of cells

Charge held at interfacial double layer at a porous carbon

material with an aqueous electrolyte

Carbon – various forms find application in energy storage

Electrochemical Capacitor
 Two carbon rods in salt water
 Initially no measurable voltage between two
electrodes
 Switch is closed, current flows from one to other
by a battery
 Charge separation at each liq./solid interface
 Persistence voltage – after switch is opened –
energy stored
 Solvated ions in electrolyte attracted to the surface
by an equal but opposite charge - double layer
 Charge separation – measured in molecular
dimensions – few Å
 Surface area - ~ 1000 m2g-1 - 5 kF
J. R. Miller, P. Simon, Electrochem. Soc. Interface 17 (2008) 31.

7
 10-06-2023

Electrochemical Capacitor
 Highly porous & high surface area electrode –
high capacitance & slow response compared to
conventional capacitors
 Cylindrical nanopore in a carbon electrode
 Charge stored near pore mouth - accessible
through short path with small electrolyte resistance
 Charge stored deeper within the pore – travel
longer electrolyte path – high series resistace
 Overall response – multiple-time-constant
equivalent circuit model

Operating voltage of capacitor – limited by breakdown potential of electrolyte (1-3 V)

For practical applications – series connected to meet the voltage requirements

Electrochemical Capacitor

Two types of capacitance

• Electric double layer capacitance (EDLC)

• Psuedocapacitance or Supercapacitors

8
 10-06-2023

Electric Double Layer Capacitor (EDLC)

• A metal/conductor in contact with liquid/solid ionic-conductor – charge
accumulation electrostatically on either side of interface – double layer
formation

• No charge transfer across the interface

• Current observed – displacement current due to rearrangement of

charges

• Non-faradaic

• Operation by charging & discharging of interfacial electrical double layer

• Electrons involved are itinerant conduction band electrons of metal or

carbon

• Eg. – Carbon
A. K. Shukla, S. Sampath, [Link], Curr. Sci. 79 (2000) 1656.

P. Jampani, A. Manivannan, P. Kumta, Electrochem. Soc. Interface 19 (2010) 57.

9
 10-06-2023

Carbon in relatively, not entirely,

unreactive

Potential voltage range of 1 V in

aqueous and 3.5 V in non-aqueous

P. Simon, A. Burke, Electrochem. Soc. Interface (2008)

Psuedocapacitor
• Energy storage through electron transfer reactions – behave capacitive

• Faradaic

• Energy storage by highly reversible surface redox reactions in addition

to EDLC – pseudocapacitive storage

• Non-faradaic

• Charge & discharge involve transfer of electric charge between phases

without any bulk phase transformation (as in battery)

• Electrons involved are transferred to or from valence electron states of

the redox cathode or anode reagent

• Eg. – Transition metal oxides : RuO2, MnO2, etc.

A. K. Shukla, S. Sampath, [Link], Curr. Sci. 79 (2000) 1656.

10
 10-06-2023

Psuedocapacitor
• Capacitance, C = Cdl + C

Cdl - electric double layer capacitance

C - pseudocapacitance

Cdl = A/4t

 - dielectric constant of electrical double layer region

A – surface area of the electrode

t – electrical double layer thickness

A. K. Shukla, S. Sampath, [Link], Curr. Sci. 79 (2000) 1656.

B. E. Conway, J. Electrochem. Soc. 387 (1991) 1539.

Psuedocapacitor

B. E. Conway, J. Electrochem. Soc. 387 (1991) 1539.

11
 10-06-2023

Psuedocapacitor

P. Simon, Y. Gogotsi, Nature Mater. 7 (2008) 845.

Psuedocapacitor

B. E. Conway, J. Electrochem. Soc. 387 (1991) 1539.

12
 10-06-2023

K. Naoi, P. Simon, Electrochem. Soc. Interface 17 (2008) 34.

13
 10-06-2023

Piezoelectric Materials
• Piezo (Greek) – to press
• The piezoelectric effect - discovered in 1880 by Pierre Curie and
Jacques Curie
• Piezoelectric materials - unique properties of electromechanical
coupling
• Generation of electric charge under an applied mechanical stress -
direct piezoelectric effect
• Induction of mechanical strain due to an applied electric field -
converse piezoelectric effect.
• Direct piezoelectric effect - essential for sensing and energy harvesting
where the applied stresses are used to
generate surface charges on the piezoelectric materials

28

14
 10-06-2023

Piezoelectric Materials

Piezoelectric constituent equation

• D – Electric field displacement

• E – Electric component
•  - Strain component
•  - Stress component
•  - Dielectric constant
• s – Elastic compliance
• d – Piezoelectric coefficient

Piezoelectric Materials
ZnO - Wurtzite

VOC and ISC by impact under human palm

15
 10-06-2023

Piezoelectric Materials

MoS2

-PVDF (Polyvinylidene
fluoride)
PZT - Pb(Zr,Ti)O3

Piezoelectric Materials - Applications

Wearable energy harvesting

16
 10-06-2023

Piezoelectric Materials - Applications

Implantable energy harvesting

Piezoelectric Materials - Applications

Wireless temperature and humidity sensor, energy storage devices

17
 10-06-2023

Thermoelectric Materials

 = Seebeck Coefficient (or) thermopower

 Peltier Coefficient
 Metals = few V K-1
 Semiconductors = few 100 V K-1  = T

T. M. Tritt, Encyclopedia of Materials: Sci. & Tech. , 2002 35

Thermoelectric Materials
𝜶𝟐 𝝈𝑻 𝜶𝟐 𝑻
𝒁𝑻 = =
 𝝆

ZT = Figure of merit
 = Seebeck coefficient
 = electrical conductivity
 = electrical resistivity
 = total thermal conductivity
total = L + E
L = lattice contribution
E = electronic contribution
T. M. Tritt, Encyclopedia of Materials: Sci. & Tech. , 2002 36

18
 10-06-2023

Characteristics of a good thermoelectric:

 Narrow band gap semiconductor (Eg = 0.25 eV @ 300 K)

 High carrier mobility ( = 2000 cm2.V-1.S-1)
 Minimum thermal conductivity ()

Phonon-glass, electron-crystal (PGEC)

Thermal conductivity like in glass or amorphous material

Electrical conductivity like in crystal

37

Thermoelectric Materials

38
T. M. Tritt, H. Böttner, L. Chen, MRS Bull. 33 (2008) 366.

19
 10-06-2023

Thermoelectric Materials
TE materials for direct solar thermal energy conversion

39
T. M. Tritt, H. Böttner, L. Chen, MRS Bull. 33 (2008) 366.

Thermoelectric Materials

[Link]
power-generators-for-sale/

20
 10-06-2023

Thermoelectric Materials
• NASA’s Cassini space craft
• Launched in 1997
• Radioisotope Thermoelectric Generator (RTG)
• Plutonium-238 as plutonium dioxide
• Temperature difference between the Plutonium-238 hot
fuel and cold environment of space
• Use thermoelectric device – to convert into electrical
energy

[Link]

21