Advanced Electricity Infrastructure Workshop

GCEP, Stanford, CA, 1 November2007

QUANTUM WIRES
FOR GRID APPLICATIONS

MATTEO PASQUALI
Department of Chemical & Biomolecular Engineering,
Department of Chemistry,
Carbon Nanotechnology Laboratory,
The Smalley Institute for Nanoscale Science & Technology
Rice University, Houston, TX
mp@rice.edu
OUTLINE

Team Rick Smalley

Energy challenge and power transmission
Carbon Nanotubes
Armchair Quantum Wire
Expected features
Progress so far
Production of
single-chirality nanotubes
Separation of nanotubes
Spinning of nanotube fibers
Perspective
Wade
Adams
TEAM
Team effort
Though process initiated by Rick Smalley & Wade Adams
Idea of the AQW: Rick Smalley et al.
Multidisciplinary, integrated project
Chemistry, Physics, Chem. Eng., Materials Science Hauge
Jim Tour, MP, Boris Yakobson, Andy Barron, Jun Kono,
Bob Hauge, Howard Schmidt, Wen-Fang Hwang, et al

Schmidt

Tour Yakobson Barron Kono

Hwang
RICK SMALLEY’S LECTURE QUIZ

Humanity’s Top Ten Problems

for next 50 years

1. ENERGY
2. WATER
3. FOOD
4. ENVIRONMENT
5. POVERTY
6. TERRORISM & WAR
7. DISEASE
8. EDUCATION
9. DEMOCRACY 2007 6.6 Billion People
2050 9-11 Billion People
10. POPULATION
THE ENERGY REVOLUTION

Smalley’s Terawatt Challenge

50 2003 50 2050
45 45
40 14 Terawatts
40
35
30 210 M BOE/day 35
25 30 30 -- 60 Terawatts
20 25 450 – 900 MBOE/day
15 20
10
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Energy:

r,
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The Basis of Prosperity
20st Century = OIL
21st Century = ?? Source: International Energy Agency
SOLAR CELL LAND AREA REQUIREMENTS

Nate Lewis
Cal Tech

Total average daily solar flux: 165,000 TW

6 Boxes at 3.3 TW each = 20 TW
Boxes are in deserts, far from population centers…
US RENEWABLE RESOURCES MAP

GEO SUN

Source: NREL
BIO WIND

Biomass potential: negative energy balance?

Harvesting of renewables far from population centers
US POWER PLANT MAP

Currently, power is generated close to population centers

Source: DOE & Nate Lewis, Caltech

Currently, power plants are near population centers

Reason: limitations on long-distance power transmission
Nuclear is a potential alternative: undesirable near cities
GLOBAL ELECTRICAL ENERGY GRID

Idea of a global grid introduced by Buckminster Fuller (~1970)

Will be made of Fullerenes?
ALLOTROPES OF CARBON
SWNT: ROLLED-UP SHEET OF GRAPHITE
 SWNTs AS A CLASS OF MATERIALS
Chirality (n,m) identifies
Michael Ströck

the species

(n,0) and (0,m): zig-zag

(n,n): armchair
(n,m): chiral

•Metallic: n = m (bandgap = 0 eV)

•Semi-metallic: n – m is multiple
of 3 (“mod 3 tubes,” bandgap ~1-
10 meV)
•Semiconducting: n – m is not a
multiple of 3 (bandgap ~0.5 - 1.0
eV; HiPco 0.8-1.4 eV)

Current methods produce mixtures of

metallic/semi-metallic (1/3rd) and semiconductors (2/3rd)
Length is polydisperse
Physical and chemical polydispersity
SWNT PROPERTIES
Exceptional mechanical strength
Tensile strength > 37 GPa
(Steel 2 GPa, PBO 5.7 GPa, Aluminum 0.3 GPa)
Young modulus ~ 0.62 – 1.25 TPa
(Steel 0.3 TPa, PBO 0.36 TPa, Aluminum 0.07 TPa)
Low density ~ 1.4 g/cm3
(Steel ~8 g/cm3, PBO 1.6 g/cm3, Aluminum 2.7 g/cm3)
Electrical resistivity ~ 1 μΩ cm
(Copper 1.7 μΩ cm, Silver 1.55 μΩ cm, Al 2.7 μΩ cm)
Thermal conductivity ~ 3000 W / m K
(Diamond ~ 2000 W / m K)
The ultimate polymer
The ultimate carbon material
Review by Baughman et al., Science, 297, 787 (2002)
CONDUCTIVITY OF SWNTs

Measurements on individual
metallic SWNT on Si wafers with
patterned metal contacts
Single tubes can pass 20 uA for
hours
Equivalent to roughly a billion amps
per square centimeter!
Conductivity measured twice that of
copper
Ballistic conduction at low fields
with mean free path of 1.4 microns
Similar results reported by others
Despite chemical contaminants and
asymmetric environment

Dekker, Smalley, Nature, 386, 474-477 (1997). McEuen, et al, Phys.Rev.Lett.84, 6082
RESONANT QUANTUM TUNNELING

Buldum and Lu,

Phys. Rev. B 63,
161403 R (2001).

Conductance in parallel end-to-end contact ~ single SWNT

Misalignment reduces conductance (up to ~10 times)
THE ARMCHAIR QUANTUM WIRE
Cable of all-aligned armchair SWNTs
Exceptional potential current carrying capacity
Estimated >1 Billion Amps / cm2 (McEuen et al, IEEE Trans.
Nanotech., 1, 78, 2002)
Current technology (steel reinforced aluminum) has
1000-5000 Amps / cm2
Combination of
High electrical conductivity (~ twice copper at RT)
High thermal conductivity (~ diamond)
High stiffness: Young Modulus ~0.6-1 TPa
Steel 0.3 TPa, Aluminum 0.07 TPa
Low density: 1.4 g/cm3
Steel 8 g/cm3, Aluminum 2.7 g/cm3
Review by Baughman et al., Science, 297, 787 (2002)
ARMCHAIR QUANTUM WIRE PROJECT
Expected Features
1-10x Copper Conductivity
6x Less Mass
Stronger Than Steel
Zero Thermal Expansion
30x Power Density vs. Cu/Al

Key Grid Benefits

Reduced Power Loss
Low-to-No Sag
Reduced Mass
Higher Power Density

SWNT Technology Benefits

Type & Class Specific
Higher Purity
Lower Cost
Polymer Dispersible
EXPECTATIONS: AQW ON THE GRID

Key Benefits
• Eliminate Thermal Failures
• Reduce Wasted Power
• Reduce Urban R.O.W. Costs
• Enable Remote Generation
MAKING THE AQW

What needs to be done:

Go from single SWNT
to macroscopic material
All-armchair SWNTs
preferably all same type
Large quantity
Align and transform into fiber
THREE WAYS OF GETTING IT DONE

Route #1:
Sort large amount of armchair SWNTs
Process into fibers
Route #2:
Sort minute amount of armchair SWNTs
Clone
Process into fibers (maybe on the fly)
Route #3:
Grow directly SWNTs of single-chirality by
tuning catalyst (variant of cloning)
Process into fibers (maybe on the fly)
ARMCHAIR QUANTUM WIRE PROJECT

initial sorting cutting fiber

SWNT & & spinning
supply separations cloning
100 X 1%
modulus
HiPco strength
CoMoCAT 1 ng density
Laser-oven 99% electrical cond.
Carpets 7 pass: thermal cond.
… 100 kg
1g
(enriched)

property maps
applications
prototype y
applications
x
SOA: SWNT TYPE SEPARATION METHODS

Selective elimination by electrical breakdown –

Collins et al., Science 2001
Covalent functionalization – Strano et al., Science 2003
Selective adsorption – Chattopadhryay et al., JACS 2003
Ion exchange chromatography – Zheng et al., Science 2003
Electrophoresis – Heller et al., JACS 2004
Density gradient ultracentifugation –
Arnold et al., Nature Nanotech. 2006
Dielectrophoresis – Krupke et al., Science 2003

Separation very difficult

Low solubility
Minimal physicochemical differences (except DEP)
Some methods appear scalable, but not highly selective
Other methods have high selectivity, poor scalability
Modeling may help scale-up
DENSITY GRADIENT ULTRACENTRIFUGATION
Sort by density
SWNTs of different diameter
have (slightly) different density
Does not quite sort by type
Possible when few SWNTs present
(e.g., CoMoCAT)

Hersam Arnold et al, Nature Nanotech,1, 60 2006

SOA: SINGLE-CHIRALITY CATALYTIC GROWTH
Growth of single type from specific catalyst
Current opinion: SWNTs grow out of liquid metal droplets (catalyst)
Droplet (particle) size controls SWNT size
Narrowest distribution: CoMoCAT
Templated substrate
Selectivity by diameter
How to go from diameter to type?

Resasco CoMoCAT

HiPco
SOA: SEEDED GROWTH/CLONING

Amplification of SWNTs
Docking: reduce catalyst particle at end
of SWNT with minimal etching,
leaving activated catalyst in intimate
contact with SWNT
Growth: cause the seed to grow
in a CVD chamber. Longer
SWNT should be identical to original
one (seed)

Smalley, Tour, Barron, et al, Rice U

SOA: SEEDED GROWTH/CLONING
Smalley et al, JACS 2006

Seed: 200nm long; amplified: 6.7 μm long

Seed and amplified SWNT have same diameter (~0.7 nm)
Same chirality not yet proven
Low yield: few seeds regrow on surfaces; looking for alternatives
SOA: SPINNING OF SWNT FIBERS
Four main methods
From water-surfactant suspension (Poulin et al, CNRS Bordeaux)
General route; SWNT manufacturing unimportant
Some surfactant/polymer may remain in fiber
From a carpet/forest (Baughman et al, UT Dallas)
Poulin
Will be great if cloning is done on carpets
Works for long CNTs (~1 mm OK)
Never demonstrated on SWNTs
From gas-phase reactor (Windle et al, Cambridge)
Will be great if “magic” catalyst can be found Baughman
Will work for long SWNTs (~1 mm OK)
From LC solution (Rice U)
General route; SWNT manufacturing unimportant
Will work for medium-length SWNTs
(~1 μm proven, maybe ~10 μm) Windle
SPINNING FIBERS FROM WATER-SURFACTANT
Poulin et al, CNRS Bordeaux

charged group 25 μm
(sulfate)

SWNT

hydrophobic
(C-12 chain)
Vigolo et al, Science 290, 1331 (2000)
SPINNING FIBERS FROM A CARPET
Baughman et al, UT Dallas

Zhang et al, Science 306, 1358 (2004)

DIRECT FIBER SPINNING FROM FURNACE
Windle et al, U Cambridge (UK)

Li et al, Science 304, 276 (2004)

SWNT-ACID LIQUID CRYSTAL

Acid protonate the SWNTs: stabilization

A liquid crystal forms at high SWNT
concentration
Similarities with rodlike polymers (Kevlar)
Liquid crystal morphology depends on 600 ppm wt. 6% wt.
type of acid (sulfuric vs. chlorosulfonic)
20 μm
Stable for months; no chemical reactions

ISOTROPIC LIQUID
DILUTE SEMIDILUTE CONCENTRATED CRYSTALLINE

Ramesh et al, J. Phys. Chem. B, 2004

7% wt in ClHSO3, cross polars, 0 and 90°
Davis et al, Macromolecules, 2004
FIBERS FROM SWNT/ACID

Highly aligned fibers; diameter ~20-70 μm

Continuous process
Ericson et al, Science, 2004
TYPICAL ACID-SPUN SWNT FIBER

Ø=37±3µm

Ø=50±2µm

Excellent macrostructure
Poor mesostructure (bundles), will affect transport
ASSESS WAYS OF GETTING IT DONE

Route #1: Flow-DEP

Separate large amount of SWNTs
Process into fibers
Large scale separation for fiber spinning
We need a miracle (breakthrough)
We know a few places where to look
Flow-dielectrophoresis
Selective reactions
Fiber spinning
We have two routes: surfactant, acid
Each needs scientific engineering
ASSESS WAYS OF GETTING IT DONE
Route #2:
Separate minute amount of SWNTs
Clone
Process into fibers (maybe on the fly)
Small scale separation
We have a route: CoMoCAT
+ density gradient ultracentrifugation
Cloning
Concept ~ proven (on surfaces, chirality?)
We need a miracle (breakthrough)
We know where to look
Fiber spinning
Two routes: surfactant, acid
Maybe carpet and/or direct
ASSESS WAYS OF GETTING IT DONE
Route #3:
Grow directly SWNTs of single-chirality by
tuning catalyst (variant of cloning)
Process into fibers (maybe on the fly)
Most elegant route
Fundamental understanding of
SWNT growth still evolving
Current understanding:
liquid phase catalyst
diameter selectivity possible
type selectivity unlikely
gas
Fiber spinning
Two routes: surfactant, acid liquid
C
Maybe carpet and/or direct
SUMMARY ASSESSMENT
Direct single-chirality growth
We need a miracle
We don’t know where to look
Cloning
Sort-of proven (surface, chirality?)
We need a miracle
We know where to look
Fiber spinning
We have four routes
Need scientific engineering
Need
Bright, enthusiastic people
Funding
RICK SMALLEY’S LECTURE QUIZ

Humanity’s Top Ten Problems for next 50 years

1. ENERGY
2. WATER
3. FOOD
4. ENVIRONMENT
5. POVERTY
6. TERRORISM & WAR
7. DISEASE
8. EDUCATION
9. DEMOCRACY
2003 6.5 Billion People
10. POPULATION 2050 10-12 Billion People
POPULATION
National
Geographic
Nov 2002
POPULATION

For the first time in history, we now live in a small island

Fully connected, interdependent
Nowhere to go (for a long time)
Insular civilizations (Jared Diamond) Diamond
Expanded and overtaxed environment until they collapsed
Learned to control harvest rate and limited population
Technology only makes the problem worse
Creates transient “excess” of resources
Albert Bartlett, “The Essential Exponential”
dx
If = kx then
dt lim x(t ) = ∞, ∀ k > 0
t →∞ Bartlett
POPULATION

Quick mnemonic: at k% growth rate, the doubling time

is Td = 100 ln2/k = 70/k
At 1% population growth rate:
At 2 kW/person, we run out of solar power in
1) 100 years (AD 2100)
2) 1,000 years (AD 3000)
3) 10,000 years (AD 12000)
4) 100,000 years (AD 102,000)
5) Ridiculous: we cannot possibly run out of solar power!
POPULATION

Quick mnemonic: at k% growth rate, the doubling time

is Td = 100 ln2/k = 70/k
At 1% population growth rate:
At 2 kW/person, we run out of solar power in
1) 100 years (AD 2100)
2) 1,000 years (AD 3000)
3) 10,000 years (AD 12000)
4) 100,000 years (AD 102,000)
5) Ridiculous: we cannot possibly run out of solar power!

At that time, we will have 2 m2/person of space!

At 0.5% population growth rate, we run out of solar
power (and space) in AD 4000!
POPULATION

Current estimates predict that population growth will stop

in about 70 years
Estimates of population growth
are highly inaccurate beyond
average life expectancy
(currently ~ 65 yr)
Situation is better now PREDICTED

than in the 1960s

We need to remain
conscious of it
CONTRIBUTORS

PhD Students: Virginia Davis, Lars Ericson, Hua Fan, Nick Parra-Vasquez,
Richard Booker, Yuhuang Wang, Naty Behabtu
UG Students: J. Sulpizio, Valentin Prieto, Jason Longoria, Robby Pinnick, Jon Allison
Postdocs: Pradeep Rai, Haiquing Peng, S. Ramesh, Rajesh Saini, Micah Green
Scientists: Carter Kittrell , Wen-Fang Hwang, Howard Schmidt
Rice Faculty: Boris Yakobson, Ed Billups, Wade Adams, Robert Hauge, Rick Smalley
U. Penn: Jack Fischer, Karen Winey, Wei Zhou, Juray Vavro, Cszaba Guthy
ACKNOWLEDGEMENTS
FUNDING
Office of Naval Research / DURINT
Air Force Office of Scientific Research
Air Force Research Lab
National Science Foundation
NASA
Welch Foundation
Texas Advanced Technology Program
REFERENCES (email mp@rice.edu)
Phase Behavior and Rheology:
Davis et al., Macromolecules, 37, p. 154 (2004)
Zhou et al., Phys. Rev. B, 72, 045440 (2005)
Pasquali et al., US Patent 6,962,092 (2005)
Parra-Vasquez et al., Macromolecules, 40, p. 4043 (2007)
Solubility and Protonation:
Ramesh et al., J. Phys. Chem B, 108, p. 8794 (2004)
Rai et al., J. Am. Chem. Soc., 128, p. 591 (2006)
Fiber Spinning and Properties
Ericson et al., Science, 305, p. 1447 (2004)
Wang et al., Chem. Mater., 17, p. 6361 (2005)
Smalley et. al., US Patent 7,125,502 (2006)
RICK SMALLEY

Be a scientist, save the world!