The wondrous world

of carbon nanotubes
Final Presentation IFP 2
February 26, 2003
Group members:




Client:
Prof. P.H.L. Notten (Philips / TU/e)
ir. R.A.H. Niessen (Philips)

Tutor:
X.E.E. Reynhout
IFP group 2
M.Daenen (N) P.G.A.Janssen (ST)
R. de Fouw (ST) K. Schouteden (N)
B. Hamers (ST) M.A.J. Veld (ST)
Overview
Introduction
Synthesis & Purification
Overview of applications
Single nanotube measurements
Energy storage
Molecular electronics
Conclusion and future outlook
Introduction: common facts
Discovered in 1991 by Iijima
Unique material properties
Nearly one-dimensional structures
Single- and multi-walled
Introduction: nanotube structure
Roll a graphene sheet in a certain direction:
Armchair structure

Zigzag structure

Chiral structure

Defects result in bends and transitions
Introduction: special properties
Difference in chemical reactivity for
end caps and side wall
High axial mechanical strength
Special electrical properties:
Metallic
Semi conducting

Synthesis: growth mechanism
Metal catalyst
Tip growth / extrusion growth







Synthesis: overview
Commonly applied techniques:
Chemical Vapor Deposition (CVD)
Arc-Discharge
Laser ablation

Techniques differ in:
Type of nanotubes (SWNT / MWNT / Aligned)
Catalyst used
Yield
Purity

Synthesis: CVD
Gas phase deposition
Large scale possible
Relatively cheap
SWNTs / MWNTs
Aligned nanotubes
Patterned substrates
Synthesis: arc discharge
MWNTs and SWNTs
Batch process
Relatively cheap
Many side-products
Synthesis: laser ablation
Catalyst / no catalyst
MWNTs / SWNTs
Yield <70%

Use of very strong laser
Expensive (energy costs)
Commonly applied
Purification
Contaminants:
Catalyst particles
Carbon clusters
Smaller fullerenes: C
60
/ C
70

Impossibilities:
Completely retain nanotube structure
Single-step purification

Only possible on very small scale:
Isolation of either semi-conducting SWNTs





Purification: techniques
Removal of catalyst:
Acidic treatment (+ sonication)
Thermal oxidation
Magnetic separation (Fe)

Removal of small fullerenes
Micro filtration
Extraction with CS
2

Removal of other carbonaceous impurities
Thermal oxidation
Selective functionalisation of nanotubes
Annealing
Overview of potential
applications
< Energy storage:
Li-intercalation
Hydrogen storage
Supercaps
> FED devices:
Displays

< AFM Tip
> Molecular electronics
Transistor
< Others
Composites
Biomedical
Catalyst support
Conductive materials
???
Overview of potential
applications
< Energy storage:
Li-intercalation
Hydrogen storage
Supercaps
> FED devices:
Displays

< AFM Tip
> Molecular electronics
Transistor
< Others
Composites
Biomedical
Catalyst support
Conductive materials
???
Overview of potential
applications
< Energy storage:
Li-intercalation
Hydrogen storage
Supercaps
> FED devices:
Displays

< AFM Tip
> Molecular electronics
Transistor
< Others
Composites
Biomedical
Catalyst support
Conductive materials
???
Energy Storage
Experiments & Modelling
Electrochemical Storage of Lithium
Electrochemical Storage of Hydrogen
Gas Phase Intercalation of Hydrogen
Supercapacitors
Energy Storage
3-electrode cell
- + -
2
reduction
oxidation
CNT H O e CNT H OH x x x x + + + +
( )
+ -
2
reduction
oxidation
Ni OH NiOOH H e

+ +

Work Electrode
Counter Electrode
Lithium Electrochemical Model
Equilibrium saturation
composition for graphite:
LiC
6

Purified SWNT bundles:
Li
1.7
C
6

Ball-milled SWNTs:
Li
2.7
C
6
20 min
10 min
0 min
Lithium Electro Chemical
Lithium Electro Chemical
Etching
Two types: lengths of 4 and
0.5 m
Good C
rev
(Li
2.1
C
6
)
Smaller hysteresis

Cut SWNTs have better
properties concerning Li
intercalation

V
o
l
t
a
g
e

[
V
]

Hydrogen Electrochemical
Lennard Jones Potential
( )
12 6
H-H H-H
LJ H-H
4 U r
r r
o o
c
(
| | | |
=
(
| |
\ . \ .
(

Hydrogen Electrochemical
storage model
Model of Hydrogen Storage at
room temperature for different
diameters of SWNTs
Hydrogen Electrochemical
Charging & Discharging
Charge Discharge Cycle
Hydrogen Electrochemical
Many contrasting conclusions:
Positive Ranging from: 0.4 2.3 wt% H
Negative: No systematic relationship
between purity and storage storage not
due to SWNTs
More investigations on the mechanism
of storage are needed in order to
explain this wide range of results
Gas Phase Intercalation of
Hydrogen model
Gas Phase Intercalation of
Hydrogen
Contrast in results is very high: range
from 0-67 wt%
Reasonable range: 2-10 wt%
More modelling needed
To compare models they have to use
the same parameters
Super Capacitor
Electrochemical double layer
Electrode (+) Electrode (-)
Separator
Molecular electronics
FEDs
CNTFETs
SETs
Field Emitting Devices
Single Emitter
Film Emitter
Field Emitting Devices
Single Emitter
Film Emitter
Field Emitting Devices
Single Emitter
Film Emitter
Patterned Film Field Emitters
Etching and
lithography
Conventional CVD
Soft lithography
Transistor Principle in
CNTFETs
Transistor
CNTFET
Doping of CNTs
Single Electron transistor
Conclusions
Mass production is nowadays too expensive
Many different techniques can be applied for
investigation
Large scale purification is possible
FEDs and CNTFETs have proven to work
and are understood
Positioning of molecular electronics is difficult
Energy storage is still doubtful, fundamental
investigations are needed