Nanotechnology and Energy: Armchair Quantum Wires

1. Nanotechnology and Energy: Armchair Quantum Wires The Power Conference ‘06 UH - GEMI June 29 , 2006 BE A SCIENTIST -- SAVE THE WORLD Wade Adams, Howard Schmidt, Bob Hauge, Amy Jaffe, and Rick Smalley* www.nano.rice.eduwww.rice.edu/energy*deceased

2. Professor Richard E. Smalley1943 - 2005Nobel Prize in Chemistry 1996 A 6 week summer project in 1985 2 – page paper in Nature C60 Buckminster- fullerene: Buckyballs with Robert F. Curl and Harold Kroto

3. National Nanotechnology ProgramWhite House – November 2003 Lonely Academic

4. Humanity’s Top Ten Problemsfor next 50 years • ENERGY • WATER • FOOD • ENVIRONMENT • POVERTY • TERRORISM & WAR • DISEASE • EDUCATION • DEMOCRACY • POPULATION 2003 6.5 Billion People 2050 8-10 Billion People

5. The ENERGY REVOLUTION (The Terawatt Challenge) 14 Terawatts 210 M BOE/day 30 -- 60 Terawatts 450 – 900 MBOE/day Energy: The Basis of Prosperity 20st Century = OIL 21st Century = ??

6. Energy-efficient Commuting

7. PRIMARY ENERGY SOURCESAlternatives to Oil TOO LITTLE • Conservation / Efficiency -- not enough • Hydroelectric -- not enough • Biomass -- not enough • Wind -- not enough • Wave & Tide -- not enough CHEMICAL • Natural Gas -- sequestration?, cost? • Gas Hydrates -- sequestration?, cost? • Clean Coal -- sequestration?, cost? NUCLEAR • Nuclear Fission -- radioactive waste?, terrorism?, cost? • Nuclear Fusion -- too difficult?, cost? • Geothermal HDR -- cost ? , enough? • Solar terrestrial -- cost ? • Solar power satellites -- cost ? • Lunar Solar Power -- cost ?

8. 165,000 TW of sunlight hit the earth every day

9. PV Land Area Requirements Nathan S. Lewis, California Institute of Technology 3 TW 20 TW

10. Solar Cell Land Area Requirements Nathan S. Lewis, California Institute of Technology 6 Boxes at 3.3 TW Each = 20 TWe

11. ≥ 20 TWe from the Moon “Harvested Moon” David Criswell Univ. Houston

12. Renewable Resource Maps Renewable sources generally remote from major population centers Source: NREL

13. US Power Production Map Currently, power is generated close to population centers Source: DOE & Nate Lewis, Caltech

14. One World Energy Scheme for 30-60TW in 2050:The Distributed Store-Gen Grid • Energy transported as electrical energy over wire, rather than by transport of mass (coal, oil, gas) • Vast electrical power grid on continental scale interconnecting ~ 100 million asynchronous “local” storage and generation sites, entire system continually innovated by free enterprise • “Local” = house, block, community, business, town, … • Local storage = batteries, flywheels, hydrogen, etc. • Local generation = reverse of local storage + local solar and geo • Local “buy low, sell high” to electrical power grid • Local optimization of days of storage capacity, quality of local power • Electrical grid does not need to be very reliable, but it will be robust • Mass Primary Power input to grid via HV DC transmission lines from existing plants plus remote (up to 2000 mile) sources on TW scale, including vast solar farms in deserts, wind, NIMBY nuclear, clean coal, stranded gas, wave, hydro, space-based solar…”EVERYBODY PLAYS” • Hydrogen, methanol, ethanol are transportation fuels • Transition technology – Plug-in Hybrids

15. Energy Nanotech Grand Challengesfrom Meeting at Rice University May 2003Report available! • Photovoltaics -- drop cost by 100 fold. • Photocatalytic reduction of CO2 to methanol. • Direct photoconversion of light + water to produce H2. • Fuel cells -- drop the cost by 10-100x + low temp start. • Batteries and supercapacitors -- improve by 10-100x for automotive and distributed generation applications. • H2 storage -- light weight materials for pressure tanks and LH2 vessels, and/or a new light weight, easily reversible hydrogen chemisorption system • Power cables (superconductors, or quantum conductors) with which to rewire the electrical transmission grid, and enable continental, and even worldwide electrical energy transport; and also to replace aluminum and copper wires essentially everywhere -- particularly in the windings of electric motors and generators (especially good if we can eliminate eddy current losses).

16. CarbonNanotechnologyLaboratoryMaking Buckytubes“Be All They Can Be” Founded by Rick Smalley in 2003 as a division of CNST Coordinates SWNT Research with 10 Faculty in 6 Departments Prof. James M. Tour – DirectorProf. Matteo Pasquali – Co-Director Dr. Howard K. Schmidt - Executive DirectorDr. Robert H. Hauge - Technology Director

17. If it ain’t tubes, we don’t do it!

18. Why Single Wall Carbon Nanotubes? MOLECULAR PERFECTION & EXTREME PERFORMANCE • The Strongest Fiber Possible. • Selectable Electrical Properties • Metallic Tubes Better Than Copper • Semiconductors Better Than InSb or GaAs • Thermal Conductivity of Diamond. • The Unique Chemistry of Carbon. • The Scale and Perfection of DNA. • The Ultimately Versatile Engineering Material.

19. Graphene SheetTexas Chicken Wire

20. SWNT: ROLLED-UP SHEET OF GRAPHITE

21. World’s largest SWNT model RAJAT DUGGAL (inside giant SWNT model) • 22 April 2005, Guinness World Record • Model of a 5-5 SWNT • ~65,000 pieces • 360 m long, 0.36 m wide • about 100 builders • over 1000 in attendance • “Supremely Silly” (from Rick Smalley) Cost of the parts: $6,000 Building a 1000-ft SWNT: pRICEless

22. Types of SWNT • Cylindrical graphene sheet • Diameters of 0.7 – 3.0 nm • Observed tubes typically < 2 nm • Both metallic and semi-conductor species possible • Length to diameter ratio as large as 104 – 105 • can be considered 1-D nanostructures armchair (a= 30°) zigzag (a= 0°) intermediate (0  a  30°)

23. Conductivity of Metallic SWNT • 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 many • Despite chemical contaminants and asymmetric environment Dekker, Smalley, Nature, 386, 474-477 (1997). McEuen, et al, Phys.Rev.Lett.84, 6082

24. Quantum Tunneling Alper Buldum and Jian Ping Lu, Phys. Rev. B 63, 161403 R (2001).

25. Tunneling Evidence • Indirect indication of conductivity by measuring lifetimes of photo-excited electrons • Cooling mechanism is interaction with phonons – just like electrical resistivity • Anomalously long life-times yield mean free path of 15 microns (10x single tubes) • Based on bundles in ‘buckypapers’ – good local symmetry and clean, but still based on mixture of metals and semi-conductors • Results imply 10 – 25x better conductivity than copper Source: Tobias Hertl, et al, Phys. Rev. Lett. 84(21) (2000) 5002

26. SWNT Quantum Wire • Expected Features • 1-10x Copper Conductivity • 6x Less Mass • Stronger Than Steel • Zero Thermal Expansion • 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

27. CNL Armchair Quantum Wire Program(armchair swnt wire with electrical conductivity > copper)( 5 years, $25 million ) • SWNT Sorting (the “signal” for the amplifier) • SWNT Amplifier • SWNT Purification • SWNT Fiber Spinning & Processing • SWNT Continuous Growth

28. Getting The Right Tube • Often Need A Single Type of SWNT • Current Growth Inadequate • Mixtures ~ 50 Types • Mixed Metals, Semi-Metals & Semiconductors • Impure & Inefficient • N,M Control Critical • Quantum Wire • Electronics & Sensors • Biomedical Therapeutics • Energy Conversion Storage • Seeded Growth Required • Separates Nucleation From Growth • Eliminate By-Products & Purification • Vastly Improved Efficiency • Sort Once at Small Scale

29. Rolling Graphite - n,m Vectors Roll-up vector

30. SWNT Excitation Fluorescence Each peak comes from a specific semi-conducting SWNT n,m value Valley of the Metals

31. SWNT Seeded Growth • Current Results • Key Starting Materials • Have FeMoC Catalyst • Have Short SWNT Seeds • Have Soluble SWNT • Key Process Steps • In-Solution Attachment • Controlled Deposition • Catalyst Docking • Reductive Etching • Growth is Next !! 1. Attach Catalyst 2. Deposit on Inert Surface 4. SWNT Growth 3. “Dock” Catalyst

32. 46 nm long 120 nm long 0.6 nm 0.6 nm 0.6 nm 1.8 nm 1.0 nm SWNTcat Growth Initial 100 mtorr CH4 – 10 min – 800 oC

33. SWNT AmplifierProcess Flow Attach Disperse Grow Dock Cut

34. SWNTamp Production Concept Hydro-carbon feedstocks Seeded Growth 500 < T < 700 C Mono-Type SWNT (1000 lb / day ) Bulk Output SWNT+ FeMoC Catalyst “Inner Loop” Processing Seed Preparation. (1 lb/ day) Cut SWNT, Prep. Catalyst, Functionalize, Attach, Dock

35. SWNT Growth Rates Science 306, 1362 (2004). Nano Lett. 4, 1025 (2004).

36. Production Scale-Up Path • Rice made 1 mg / day in 1997 • Lab-scale reactor at 1 gm / hour (2002) • CNI Pilot plant producing 20 lb /day • CNI now testing 100 lb / day reactor

37. Forming SWNT Wires • Need macro-crystalline SWNT fiber/wire • Starting material is tangled at several scales • Starting material has variety of diameters and types • Enormous Van der Waals forces make it hard to separate SWNT bundles

38. Dispersion in Super-Acids • SWNT bundles swell in superacids • Dispersion due to “protonation” & intercalation of SWNTs • V. A. Davis et. Al., Macromolecues 37, 154 (2004) in 102% H2SO4 “Spaghetti” In Oleum dried SWNT fiber W.-F Hwang and Y. Wang

39. Prototype Wire - SWNT Fibers • Producing Neat SWNT Fibers • Dry-Spun from Oleum • 6 to 14 Wt. % SWNT Dope • Extruded as 50 µm Dia. Fibers • 109 Tubes in Cross Section • 100 Meters Long Science305, 1447-1450, 3 September 2004!!!

40. Ultimate Properties of Polymers Staudinger Continuous Crystal Model Perfect orientation Perfect lateral order Few chain end defects (HMW) + INTRINSIC CHAIN PROPERTIES Hermann Staudinger, Die Hochmolekularen Organischen Verbindungen, Berlin: Springer p.111 (1932)

41. SWNT Tensile Strength Predicted tensile strength of single-wall nanotubes >100 GPa Calculated strain-to-failure >30% Measurements on small bundles found strength ~30-60 GPa Yakobson, et al., Comp. Mat. Sci.8, 341 (1997).

42. Quantum Wire on The Grid • Key Grid Benefits • Eliminate Thermal Failures • Reduce Wasted Power • Reduce Urban R.O.W. Costs • Enable Remote Generation

43. Grid Applications & Benefits • Eliminate Thermal-Sag Failure: Now a $100B+ a year problem. • Short-Distance AC: AQW could increase throughput up to ten-fold without increasing losses while using only existing towers and rights-of-way. Avoid new construction in congested urban areas – estimated over $100M per mile. • Medium-Distance AC: AQW could decrease resistive losses and voltage drop ten-fold if amperage were not increased. This would improve grid dynamics significantly in the range between 100 and 300 miles, where voltage stability limits deliverable power. • Long-Distance HVDC: AQW could permit amperage throughput ten fold or reduce losses ten-fold. New conventional lines cost $1M to $2M per mile, plus about $250M per AC/DC converter station. • Remote Power: Could enable utilization of large-scale renewables and remote nuclear.

44. High Pressure CO (HiPCO) Process NASA Success Stories Tuesday, April 26th, 2005 -- NASA Announces new $16M Grant to Rice University and two NASA Centers –Research to develop the Quantum Wire CNL Actively building new collaborations to fund this critical research program!!! Fe, Ni Catalysts CO + CO CO2 + SWNT + impurities 900-1200 C 10-40 atm Continuous process 10-100’s g/day Small diameters (0.7nm) Company spin-off (CNI) Rice Univ.  Carbon Nanotechnologies, Inc. & NASA

45. Buckytubes Offer Incredible Opportunities • Composites • Electrically conductive composites • Wide range of conductivities • Antistatic • Electrostatic dissipation • EMI/RFI shielding   • Bulk parts • Transparent conductive coatings • Anti-corrosion coatings • Reinforced composites Tougher, stronger, stiffer, wear resistant • Thermosets and thermoplastics • Parts, coatings • High performance fibers • High performance ceramics • Thermally conductive composites • Electronics packaging • Industrial applications • Energy • Fuel cells • Supercapacitors and batteries • Photovoltaic cells • “Quantum Wires” • Electronics • Field emission • Flat panel displays • Back light units • Electron device cathodes • Sensors • Printable electronics • Logic and memory devices • Interconnects

46. Roadblocks • Vision without funding is hallucination. • Da Hsuan Feng – UT Dallas • Vision without hardware is delusion. • Lockheed engineer

47. From the age of Space to the age of Medicine Age of Energy?

48. New Energy Research Program(Smalley’s Nickel & Dime Solution) • For FY06-FY10 collect 5 cents from every gallon of oil product Invest the resultant > $10 Billion per year as additional funding in frontier energy research distributed among DOE, NSF, NIST, NASA, and DoD. • For the next 10 years collect 10 cents from every gallon; invest the >$20 Billion per year in frontier energy research. • Devote a third of this money to New Energy Research Centers located adjacent to major US Research Universities, especially Zip Code 77005. • At worst this endeavor will create a cornucopia of new technologies and new industries. • At best, we will solve the energy problem before 2020, and thereby lay the basis for energy prosperity & peace worldwide.

49. Leadership • President Bush – State of the Union Address – Jan 31, 2006 • “America is addicted to oil” • Replace oil imports from Middle East by 75% by 2025 • DOE Advanced Energy Initiative 22% increase in clean energy research • Zero emission coal • Solar and wind • Clean, safe nuclear • Batteries, Hydrogen, ethanol • A BIG change from the 2001 Cheney Energy Report – drill our way to independence!

50. But… • Are these ideas tough or aggressive enough? • NO! • Biofuels budget actually smaller than in FY06 • No market signal for more efficient vehicles • Fuel economy standards – regulatory • 40 mpg in 10 years saves 2.5M BOE/day • Substantial gas tax – market mechanism • Up to Congress to execute programs • Incentives for alternate fuel production/vehicles • Funding for research initiatives