ENIC Tutorial

Hydrogen Storage
Gang Chen
Massachusetts Institute of Technology Cambridge, MA
Collaborators:
Mildred S. Dresselhaus, MIT Vincent Berube, MIT Gregg Radtke, MIT Costas Grigoropoulos, UCB Samuel Mao, UC Berkeley Xiao Dong Xiang, Intematix Taofang Zeng, NCSU
1

Sources:
Thomas Audrey, PNNL James Wang, SNL Andreas Zuttel, IfRES

Department of Energy

NanoEngineering Group

Outline
Why hydrogen economy? Hydrogen storage requirements/challenges Ways to store hydrogen Nanoscale effects on hydrogen storage

NanoEngineering Group

2

Energy Challenges: Climate Change
CO2 CH4 (ppmv) (ppmv) 325 300 275 250 500 225 200 175 400 300 800 700 600

0

- 4

- 8 380 1.5

Atmospheric CO2 (ppmv)

∆ T relative to present (°C)

-- CO2 -- CH4 -- ∆T

+ 4

Relaxation times 50% of CO2 pulse to disappear: 50 - 200 years transport of CO2 or heat to deep ocean: 100 - 200 years

400

100 200 300 Thousands of years before present (Ky before present)

0

360 340 320 300 280 260 240

-- CO2 -- Global Mean Temp

1.0 0.5 0 - 0.5 - 1.0 - 1.5

Temperature (°C)

Intergovernmental Panel on Climate Change, 2001
http://www.ipcc.ch

1000

1200

1600 1400 Year AD

1800

2000

NanoEngineering Group

3

Hydrogen Economy
Production
Biomass Hydro Wind Solar Storage is Bottleneck

Storage

Use
Transportation .

Nuclear

With Carbon Sequestration

Oil

Distributed Generation HIGH EFFICIENCY & RELIABILITY ZERO/NEAR ZERO EMISSIONS
From Patrovic & Milliken (2003) and James Wang Sandia National Laboratories 4

Coal Natural Gas

NanoEngineering Group

. 2003 "America is addicted to oil. hydrogen-powered automobiles… With a new national commitment.” President Bush. our scientists and engineers will overcome obstacles to taking these cars from laboratory to showroom.. which is often imported from unstable parts of the world. State-of the-Union Address. January 31. and pollution-free. and in pollution-free cars that run on hydrogen’ President Bush.2 billion in research funding so that America can lead the world in developing clean. 2006 NanoEngineering Group 5 .better batteries for hybrid and electric cars. January 28. so that the first car driven by a child born today could be powered by hydrogen.” “. State-of the-Union Address.“ “The best way to break this addiction is through technology.Hydrogen: A National Initiative “Tonight I'm proposing $1.

Ways to Store Hydrogen Compressed gas Liquid hydrogen Condensed state Volumetric density Gravimetric density Kinetics Heat transfer Efficiency Reversibility Operation temperature 6 Key Issues NanoEngineering Group .

15 Nov. Nature. 2001 NanoEngineering Group 7 .How large of a gas tank do you want? Volume Comparisons for 4 kg Vehicular H2 Storage Schlapbach & Züttel.

DOE Targets NanoEngineering Group 8 .

Compressed Hydrogen Gas • Type IV all-composite tanks are available at 5000 psi (350 bar) • 10.000 psi tanks being developed NanoEngineering Group 9 .

Liquid Hydrogen Storage Linde Tank. GM From Patrovic & Milliken (2003) dormancy NanoEngineering Group 10 .

Hydrogen Storage in Condensed States Physisorption Adsorption on Surface Chemisorption Absorption into Matter NanoEngineering Group 11 .

Potential Elements NanoEngineering Group 12 .

Audrey .Hydrogen Density of Materials NanoEngineering Group 13 T.

333.1 .Lennard-Jones.Desired binding energy range Potential energy for molecular and atomic hydrogen absorption Desirable range of binding energies: 10-60 kJ/mol (0.pp.6 eV) MgH2 TiH2 LiH Physisorption Low temperature NanoEngineering Group Molecular H2 Carbon physorption J.0. 2H H-I H-SH H-CH3 H-OH AlH3 0 100 200 300 400 500 Bond strength [kJ/mol] 14 Chemisorption High temperature Atomic H . 28 (1932). E. FaradaySoc. Trans.

Physisorption 1 0.8 • Langmuir Isotherm 0.2  ε  −1/ 2 K ∝T exp    k BT  NanoEngineering Group 0 0 2 10 4 4 10 6 10 PRESSURE 4 4 8 10 4 1 10 5 Assumption: Monolayer coverage 15 .6 θ θ= Kp 1 + Kp 0.4 Molecules Adsorbed θ= Number of Adsorption Site 0.

414 Vm cm3/g at STP NanoEngineering Group 16 . Emmett and E.. Teller. 60. 309 Multilayer coverage BET Area Vm N Aσ Asp = 22. 1938. Chem. Brunauer. Soc. Am.Physisorption S. P. J. H.

Research Directions Increasing surface area Increasing binding energy NanoEngineering Group 17 .

2004 NanoEngineering Group 18 . News. 2002 MOF: Rosi et al. & Eng. Chem.Increasing Surface Area Johnson. JACS.. 2003 Roswell et al.. Science.

Zhou et al. 2006 NanoEngineering Group 19 . 939. Carbon.html Boron Doping of CNT. 44.caltech.wag.Increasing Binding Energy http://www.edu/f uelcells/index.. Z.

Chemisorption NanoEngineering Group A. Zuttel 20 .

NH3BH3 MgH2 NanoEngineering Group NaAlH4 21 NH3BH3 .Classification Metal hydrides: MgH2 Complex hydrides: NaAlH4 Chemical hydrides: LiBH4.

The Hydrogen Bottleneck DOE goal (2015) Storage wt. % Storage vol.60 °C (too high) <100 atm. % Reversibility (cycle) System storage cost Fueling time (reaction kinetics) Operating temperature Operating pressure 9% 81 kg/m3 1500 cycles $2/kWh 30 s/kg-H2 (too slow) -40 . From JoAnn Milliken (2002) JoAnn Milliken (2002) Metal hydride Chemical hydride Limited $50/kWh $18/kWh NanoEngineering Group 22 .

PcT Relation NanoEngineering Group From A. Zuttel 23 .

Zuttel .Thermodynamics NanoEngineering Group 24 A.

Zuttel .Stability of Hydrides Thermodynamic Equilibrium NanoEngineering Group 25 A.

Energy Barrier Energy Energy Barrier ∆E MHx M+H2/2 Separation Thermodynamically Favorable Does Not Mean Kinetically Favorable NanoEngineering Group 26 .

3NaAlH4 Na3AlH6 + 2Al + 3H2 3.8 wt% Low hydrogen capacity and slow kinetics are issues NanoEngineering Group 27 .7 wt% 3NaH + Al + 3/2H2 1.Reversible Metal Hydride System NaAlH4 Sodium alanate doped with Ti is a reversible material hydrogen storage approach.

A.System destabilization Forming new alloys •Reduce energy (temperature) needed to liberate H2 by forming dehydrogenated alloy •System cycles between the hydrogen-containing state and the metal alloy instead of the pure metal •Reduced energy demand means lower temperature for hydrogen release. J. pp. Mechanically Doped NaAlH4 Gregory L. Zidan et al. Alloys and Compounds 285 (1999). NanoEngineering Group 28 R. Olson DOE 2005 Hydrogen Program Annual Review Doping with a catalyst •Reduces the activation energy. 119. . •Allows both exothermic and endothermic reactions to happen at lower temperature.

Zuttel NanoEngineering Group 29 .A.

1atm. A:Materials Science & Processing. No 7. Vol 79. 1765 . p.05atm) Release temperature too high and low release pressure. Orimo et al. Appl.) Li N H H H Second: Li2NH + LiH Li3N + H2 (5% @ 300c 0. .Imide (NH) and Amide (NH2) First step: LiNH2 + LiH H Li H H N Li Li Li2NH + H2 (6. Phys.1767.55% @ 300C. Li Li H Li N H Li Li N Li H H Partial Mg substitution reduces release temperature Li1-xMgxNH2 NanoEngineering Group 30 S..

Chemical Hydrides NanoEngineering Group 31 .

proprietary stabilizers Paste byproduct • Hydrogen capacity is high at around 10 wt% hydrogen.35% sol. 2Na + 2H2O → 2NaOH + H2 Polyethylene-coated pellets. • Reactions are irreversible on-board vehicle. Stabilized with 1-3% NaOH Catalyst Borax in NaOH 2LiH + 2H2O → 2LiOH + 2H2 Light mineral oil slurry. mechanically cut to expose Na NanoEngineering Group Regeneration costs are a major issue 32 From Patrovic & Milliken (2003) .Irreversible Chemical Hydrides NaBH4 + 2H2O → NaBO2 + 4H2 20 . • Dehydrogenation kinetics are fast.

Fueling Cycle From DOE BES Hydrogen Report NanoEngineering Group 33 .

NanoEngineering Group 34 .

Audrey .) NanoEngineering Group 35 T.N-Ethylcarbazole (Air Products. Inc.

Chem. J.Metal ammine complexes (kg m-3) 110 120 Mg(NH3)6Cl2 = MgCl2 + 6NH3 (9. High temperature of hydrogen release 2NH3 3H2+ N2 @ ~600K NanoEngineering Group Christensen et al.1%) @ T <620K Ammonia is toxic Can be used in high T solid oxide fuel cells... Mater. 15. 4106–4108 36 . 2005.

127 (2005) 1391-1399 Foams: Al. C. Wire mesh Klein et. etc. fins and meshes Expanded Graphite Compacts NanoEngineering Group 37 .1 W/m-K SOLUTIONS See: Zhang et. J. al. Hydrogen Energy 29 (2003) 1503-1511 Conductive foams. Heat Transfer.Thermal Management • Hyriding reaction: ~1 MW for 5 min. al. Int... J. • Nanostructured materials impair heat transfer • Temperature rise suppresses hydriding reaction • Typical hydride conductivity: k~0.

Benefits of Nanostructures Increase kinetics: diffusion time ~ radius square/diffusivity Possibility of co-existence of chemi. we can expect similar dependence in release temperature. equilibrium pressure and enthalpy of reaction change with radius.and physi-sorption Possibility of changing thermodynamic properties po • Yang’s Equation: 2σ pi − po = r • Kelvin Theory: Surface Tension Radius MHx pi NanoEngineering Group For multiphase system. equilibrium pressure and enthalpy of formation. transition temperature. For hydride. 38 .

LBNL NanoEngineering Group 39 .5 1.0 0.Mao.Simultaneous Physisorption and Chemisorption target material laser pulse 3.5 0.0 MgNi:SiO2 sorption MgNi:SiO2 desorption MgNi:SiO2 sorption (7 days) MgNi:SiO2 desorption (7 days) SiO2 sorption SiO2 desorption hydrogen uptake (wt.5 2.0 0 nanoporous sample 5 10 pressure (bar) 15 20 S.%) expanding metal vapor 2.0 1.

Increase adsorption sites due to low coordination surface atoms. r ) r  VMH  ∆ M → MH (γ . r ) = (γ MH ( r )    VM  NanoEngineering Group − γ M ( r )) + Eadsoption 40 . eq ln PH = 2 ∆H o ∆S o − RT R Nanoparticle molar free energy of formation ∆G ( r ) = ∆Go (r ) + RT ln( + 2/3 aMH ) aM PH 2 3VM ∆ M → MH (γ . surface and size affect reaction enthalpy. Increase the surface to volume ratio.Size Effects on Thermodynamic Properties Assuming the following reaction M + H2 MH2 Bulk molar free energy of formation ∆G = ∆Go + RT ln( aMH ) aM PH 2 Van’t Hoff relation At nanoscale. Lower binding energy in small metallic clusters.

r ) + r Following Tolman’s work. J. surface tension is allowed to vary with radius ∆o ∆ = a 1+ r DFT values of internal energy calculated by Wagemans et al. Soc. 127 NanoEngineering Group 41 .Am.Modeling DFT Results If internal energy dependence on radius is all contained in the surface energy term ∆E(r ) ≈ ∆EBulk 3VM ∆ M →MH (γ . 2005. Chem.

Enthalpy of Reaction eq = ln PH 2 ∆H o 3VM ∆ M → MH ∆So + − RT rRT R ∆H eff 3VM ∆ M → MH = ∆H o + r • Nanoparticles with positive ∆ will have Lower equilibrium temperature Less heat release during hydrogenation NanoEngineering Group 42 .

Surface energies and material properties at nanoscale offer ways to tune the energetics of absorption and desorption. Reducing grain and particle size increases kinetics and uptake. 43 NanoEngineering Group .Improving sorptions properties with nanotechnology The bulk hydride sorption rate is prohibitively small and release release temperature is too high.

Int. Angew. Autrey et al. Reversibility is still an issue NanoEngineering Group T. Chem. 2005. 44.44 .Nanoscafolding to improve kinetics and change thermodynamics: Borazane (NH3BH3) Nanoscaffolding improves kinetics and reduces enthalpy of formation (catalytic effect) Reduces emmissions of unwanted chemicals Scaffolding decreases H wt-% by half.. 3578 –3582. Angew. Ed.

5 Ge0.Mass and Heat Transfer • Diffusion limited hydride reaction.6 P=0. Therefore. Hydriding/dehydriding Reaction Nanoscale heat transfer H2 mass diffusion α β Nanostructured material mK) THERMAL CONDUCTIVITY (W/ • The strongly exothermic hydriding reaction increases the sample’s temperature which reduces the reaction rate or even stops the reaction altogether.BULK (FOURIER LAW) KZ.5 Cross-Plane Lines--Fitting with Chen’s Model P=0. EXPERIMENTAL KX. NanoEngineering Group 103 KX.5 BULK ALLOY (300K) 10 1 In-Plane P=0. we need to balance mass diffusion kinetics with heat transfer.FILM.6 10 0 45 80 120 160 200 240 TEMPERATURE (K) 280 . • Nanostructures usually have poor heat transfer characteristics. • Rapid hydriding reaction thus requires effective heat removal solution. EXPERIMENTAL Si0. • Optimal pore and particle sizes: balance pore diffusion and diffusion in the solid particle to control kinetics.FILM.BULK (FOURIER LAW) 10 2 KZ.

and heat transfer NanoEngineering Group 46 . Thermodynamics: sorption/desorption temperature. thermodynamics. Kinetics. mass and heat transfer: pumping time Reversibility: cycling time Nanoscale effects on storage density. kinetics.Summary Key issues: volumetric and gravimetric density.