ENERGY NANOTECHNOLOGY --- A Few Examples

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1 ENERGY NANOTECHNOLOGY --- A Few Examples Gang Chen Nanoengineering Group Rohsenow Heat and Mass Transfer Laboratory Massachusetts Institute of Technology Cambridge, MA gchen2@mit.edu

2 Thermal-Electrical Energy Conversion COEFFICIENT OF PERFORMANCE Temperature (K) REFRIGERATION Household Refrigerator Thermoelectrics Environmentally Benign Refrigeration POWER GENERATION Thermo- PV THERMODYNAMIC LIMIT Power Plant Auto Energy Efficiency Waste Heat Recovery Solar PV 0 Renewable Energy EFFICIENCY Grand Challenges: Efficiency and cost effective mass production

3 Nano for Energy Increased surface area Interface and size effects Molecules Λ = nm λ=1 nm Λ---Mean free path λ---wavelength Photons Λ > 10 nm λ= µm Electrons Λ= nm λ=10-50 nm Thermodynamics Kinetics Phonons Λ= nm λ=1 nm

4 Phonon and Electron Engineering for Thermoelectric Materials

5 Thermoelectric Devices COLD SIDE COLD SIDE - + HOT SIDE I N P HOT SIDE Nondimensional Figure of Merit Joule Heating Seebeck Coeff. Electron Cooling GPHS Radioisotope Thermoelectric Generator 2 σs T ZT = k Reverse Heat Leakage Through Heat Conduction

6 State-of-the-Art in Thermoelectrics FIGURE OF MERIT (ZT)max PbSeTe/PbTe Quantum-dot Superlattices (Lincoln Lab) Bi 2 Te 3 /Sb 2 Te 3 Superlattices (RTI) Bi 2 Te 3 alloy PbTe alloy Si 0.8 Ge 0.2 alloy (Michigan State) Skutterudites (Fleurial) Dresselhaus PbTe/PbSeTe Nano Bulk S 2 σ (µw/cmk 2 ) k (W/mK) ZT (T=300K) Harman et al., Science, 2003 Bi 2 Te 3 /Sb 2 Te 3 Nano Bulk S 2 σ (µw/cmk 2 ) k (W/mK) ZT (T=300K) Venkatasubramanian et al., Nature, YEAR

7 Heat Conduction Mechanisms Unit Cell of Superlattice Layer B Layer A Unit Cell of B Layer A New Crystal? Inhomogeneous Multilayers?

8 Heat Conduction Mechanisms in Superlattices Normalized Thermal Conductivity THERMAL CONDUCTIVITY (W/mK) BULK SPECULAR (p=1) p=0.95 Ideal Superlattices In-Plane LD Cross-Plane LD T=300K AlAs/GaAs DIFFUSE Yao 1987 (p=0) p=0.8 Yu et al Capinski et al Yao (1987) Capinski et al Yu et al. (1995) LAYER Period THICKNESS Thickness (Å) (Å) In-Plane Cross-Plane Major Conclusions: Ideal superlattices do not cut off all phonons due to pass-bands Individual interface reflection is more effective Diffuse phonon interface scattering is crucial Coherent Structures Are Not Necessary, Nor Optimal!

9 Photon Engineering: Thermophovoltaics

10 Thermophotovoltaics Heat Source Filter Photovoltaic Cells EMISSIVE POWER (W/cm 2 µm) Useful Useless 5600 K 2800 K 1500 K 800 K E WAVELENGTH (µm) G Frequency Selective Emitter Frequency Selective Filters Photon Recycling Structures Evanescent Wave Structures High Efficiency PV Cells

11 Surface Waves and Near Surface Energy Density ω Free Space Surface Modes k x Energy Density (Jm -3 ev -1 ) Wavelength (µm) d = 10 nm d = 100 nm d = 1 µm d = 10 mm Energy (ev) blackbody Energy density in the vicinity of a half-plane of BN. High Energy Density, Monochromatic EM Fields Exists Near Surfaces When ε is Equal but of Opposite Signs. But They Are Non-Emitting! Surface Plasmons and Surface Phonon Polaritons

12 Near Field Energy Conversion Wavelength (µm) d = 5 nm 8 Power absorbed (Wcm -2 ) SiC Source (BN, SiC) PV material Power absorbed 10 1 Blackbody Vacuum gap (nm) Flux (Wm -2 ev -1 ) d = 1 nm d = 0 nm d = 10 nm Frequency (ev)

13 Coupled Conduction and Radiation Nonequilibrium Thermoelectric Devices

14 Nonequilibrium Transport Conventional TE Cooler Conventional Micro TE Cooler T 2 Electron Temperature T 1 Cooling Target Thermoelectric Element T 1 Cooling Target Phonon Temperature Thermoelectric Element T 2 Battery Battery Proposed Nonequilibrium Thermoelectric Devices Explore nonequilibrium between electrons and phonons couple the cooling target with thermoelectric element without direct lattice contact ZT 2 σs T = k e + Xk p T 1 Cooling Target Vacuum Gap Electron Temperature, T e Phonon Temperature, T p Battery T 2

15 Surface Plasmon Coupling of Electrons d Model Based on Fluctuation-Dissipation Theorem d=10 nm Macroscale gap T 1 Far-Field Nanoscale gap T 1 Surface Waves Three orders of magnitude increase in energy transfer flux due to surface plasmon resonance

16 Surface-Plasmon Enabled Nonequilibrium Thermoelectric Refrigerators COLD END TEMPERATURE (K) G InSb k e /k=0.1 Z=0.002K -1 T H =300K G=10 8 W/(m 3 K) G=10 10 W/(m 3 K) G=10 12 W/(m 3 K) Conventional THERMOELECTRIC ELEMENT LENGTH (µm) COP Cooling Load q = 50 W/cm 2 G = 10 8 W/(m 3 K) G = W/(m 3 K) G = W/(m 3 K) Conventional k e /k = 0.1 Z = 0.002K -1 T H = 300K THERMOELECTRIC ELEMENT LENGTH (µm) Performance is determined by the doping concentration and operation temperature. Principle works for both refrigerators and power generators.

17 Key Points Nanoscale effects are enabling breakthroughs in energy technologies. Need cost-effective and mass producible nanotechnology for energy applications. Fundamental understanding leads to new manufacturing paradigms. Fundamental research problems exist in both individual nanostructures and mesoscopic nanostructures. Multidisciplinary research and interdisciplinary researchers are needed.

18 ACKNOWLEDGMENTS Current Members H. Asegun (Molecular Dynamics) V. Berube (hydrogen storage) Z. Chen (Metamaterials, TPV) S. Goh (polymers) T. Harris (Thermoelectrics&Nanomaterials) Q. Hao (Thermoelectrics) D. Kramer (Solar thermoelectrics) H. Lee (Thermoelectric Materials) H. Lu (TPV and PV) A. Minnich (thermoelectrics) A. Muto (nanowires and thermoelectrics) S. Nakamura (nanowires and thermoelectrics) A. Narayanaswamy (Metamaterials, TPV) G. Radtke (hydrogen storage) A. Schmidt (ps pump-and-probe) E. Skow (polymers) S. Shen (lubrication, rarefied gas dynamics) Dr. M. Chieso (nanofluids) Dr. X. Chen (thermoelectrics, Pump-and-Probe) Dr. D. Vashee (thermoelectrics) Prof. Y.T. Kang (nanofluids) Collaborators M.S. & G. Dresselhaus (MIT, NW&CNT, Theory) J.-P. Fleurial (JPL, Thermoelectric Devices) J. Joannopoulos (MIT, Photonic Crystals) Z.F. Ren (BC, Thermoelectric Materials, CNT) X. Zhang (Berkeley, Metamaterials) Past Members (Partial List) Prof. C. Dames (Nanowires, UC Riverside) Prof. D. Borca-Tasciuc (Nanowires, RPI) Prof. T. Borca-Tasciuc (Thermoelectrics,RPI) Dr. F. Hashemi (Nano-Device Fabrication) Dr. A. Jacquot (TE Device Fabrication) Dr. M.S. Jeng (Nanocomposites, ITRI) Dr. R. Kumar (Thermoelectric Device Modeling) Dr. W.L. Liu (superlattice) Dr. D. Song (TE and Monte Carlo, Intel) Dr. S.G. Volz (MD, Ecole Centrale de Paris) Prof. B. Yang (TE and Phonons, U. Maryland) Prof. R.G. Yang (Nanocomposites, U. Colorado) Prof. D.-J. Yao (TE Devices, Tsinghua Univ.) Prof. T. Zeng (Thermionics, NCSU) Sponsors: ARO, DOE, NASA, NSF, ONR, Industries

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