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Sustainable Science and Engineering Center

Hydrogen Storage Sustainable Energy Science and Engineering Center Main Market Segments

1. Utility/industrial applications including: grid reinforcement, renewables integration and uninterruptible power supply (UPS) Applications

2. Transport / mobile applications including: on-board power for , new drive trains (electric and hybrid electric vehicles) and leisure applications (caravanning)

3. Portable applications including: computing, cell-phones and cameras (the 3 ‘C’s’).

Source: Ian Edwards, ITI Energy, May 24th, 2005 Sustainable Energy Science and Engineering Center Generic Storage Systems

Electrochemical systems batteries and flow cells

Mechanical systems fly-wheels and compressed air energy storage (CAES)

Electrical systems super- and superconducting magnetic energy storage (SMES)

Chemical systems cycle (electrolysis -> storage -> power conversion)

Thermal systems sensible (storage heaters) and phase change

Source: Ian Edwards, ITI Energy, May 24th, 2005 Sustainable Energy Science and Engineering Center Potential

Energy Sources Typical Chemical Energy

Hydrogen 142.0 MJ/kg 29.7 MJ/kg 17.0 MJ/kg Automotive 45.8 MJ/kg 55.5 MJ/kg 22.7 MJ/kg

(Source: Chemical Energy, The Hyper text Book) Sustainable Energy Science and Engineering Center Energy Density

Fuel Typical Stored Chemical Energy Density

Hydrogen 7.1 MJ/kg @ 5wt% Ethanol 26.7 MJ/kg @ 90wt% Ammonia 13.6 MJ/kg @ 80wt% Automotive Gasoline 41.2 MJ/kg @ 90wt% Methane 44.5 MJ/kg @ 80wt% Methanol 20.4 MJ/kg @ 90wt%

Source: Ian Edwards, ITI Energy, May 24th, 2005 Sustainable Energy Science and Engineering Center Energy

Fuel Hydrogen weight Ambient state Liquid volumetric energy fraction energy density(MJ/L) density (MJ/kg)

Hydrogen 1 8.4-10.43 120 Methane 0.25 Gas 21(17.8)2 50 (43)2 Ethane 0.2 Gas 23.7 47.5 0.18 Gas (liquid)1 22.8 46.4 Ammonia 0.18 Gas (liquid)1 13.1 17.0 Gasoline 0.16 Liquid 31.1 44.4 Ethanol 0.13 Liquid 21.2 26.8 Methanol 0.12 Liquid 15.8 19.9

1 A gas at room temperature, but normally stored as a liquid at moderate . 2 The larger values are for pure methane. The values in parentheses are for a “typical” . 3 The higher value refers to hydrogen density at the triple point

Source: Ian Edwards, ITI Energy, May 24th, 2005 Sustainable Energy Science and Engineering Center Energy Density in wh/liter

Material Volumetric Gravimetric

Diesel 10942 Wh/l 13762Wh/kg Gasoline 9,700 Wh/l 12,200 Wh/kg LNG 7,216 Wh/l 12,100 Wh/kg Propane 6,600 Wh/l 13,900 Wh/kg Ethanol 6,100 Wh/l 7,850 Wh/kg Methanol 4,600 Wh/l 6,400 Wh/kg Liquid H2 2600 Wh/l 39,000 Wh/kg 150 Bar H2 405 Wh/l 39,000 Wh/kg 250 Wh/l 350 Wh/kg Nickel Metal Hydride 100 W·h/L 60Wh/kg Lead Acid Battery 40 Wh/l 25 Wh/kg Compressed Air 17 Wh/l 34 Wh/kg Sustainable Energy Science and Engineering Center Objective To achieve adequate stored energy in an efficient, safe and cost effective system.

Gravimetric storage density: the gravimetric storage density is the weight of the hydrogen being stored divided by the weight of the storage and delivery system proposed Source: Oak Ridge National Laboratory Shop, May 2003 Sustainable Energy Science and Engineering Center Energy Storage

1970 1980 1990 2000 2010 2020

Source: Ian Edwards, ITI Energy, May 24th, 2005 Sustainable Energy Science and Engineering Center Hydrogen Storage

Hydrogen pellets

Mg(NH3)6Cl2

1970 1980 1990 2000 2010 2020

Source: Ian Edwards, ITI Energy, May 24th, 2005 Sustainable Energy Science and Engineering Center Technology Status Sustainable Energy Science and Engineering Center Storage Methods Sustainable Energy Science and Engineering Center of (LHV)

125 0

carbon hydrogen 100

75

120

50

20 24 25 25 26 25 26 Energy Density MJ/kg 25 26 25 11 5 30 24 22 21 20 20 19 19 18 16 15 17 0

n e ) l) l a e ne ne ne ne ne ne e ni ta a tane s than tha n x oli e e e buta s di thano pe he hep a ( ethanol e m propa g e m ammo hydrog ( n e n ceta octa Sustainable Energy Science and Engineering Center Energy Densities (LHV) in Liquid state

40

carbon hydrogen 30

Hydrogen 20 18 density range 18 17 20 16 15 12 12 9 8

4

10 Energy Density (MJ/liter) 14 13 13 13 13 13 12 12 12 13 12 12 11 11 9

0

) ) l l l e e e e o ia n n n n e se tane a ie oline p xa nta water s e e e ethan th mon a h h p e hydride e (d propan methanemethanoam n (g e ta liq. hydrog ce tan c o Sustainable Energy Science and Engineering Center Compressed Gas

5 Compressed Gas Storage Density Gasoline: 13 MJ/L (300 K, LHV) 4

3

2

Energy Density (MJ/liter) 1

350 bar 700 bar 0 0 2000 4000 6000 8000 10000 Pressure (psi) Sustainable Energy Science and Engineering Center Compressed Gas

• increased pressure (>700 bar) – stronger, lighter composite tanks (cost) – hydrogen permeation – non-ideal gas behavior • conformable tanks – maximum gain ~20% (cylind./rect. ) – some increase in weight • microspheres – multiple shell volumes – close-packed packing density ~60% of volume – hydrogen release/reload mechanism Sustainable Energy Science and Engineering Center Compressed Gas Cylinders

Carbon fiber wrap/polymer liner tanks are lightweight and commercially available. weight specific energy 6 wt.% 7.2 MJ/kg 7.5 wt.% 9.0 MJ/kg 10 wt.% 12 MJ/kg Energy density is the issue: Pressure Gas density System density 350 bar 2.7 MJ/L 1.95 MJ/L 700 bar 4.7 MJ/L 3.4 MJ/L Sustainable Energy Science and Engineering Center High Pressure Cryogenic Tank

600 EOS

500

400

300

Pressure bar 200

100 S. Aceves, et al 2002

0 Estimated energy density: 20 30 40 50 60 70 80 90 100 Temperature K 4.9 MJ/L (Berry 1998)

• reduces temperature requirements • eliminates liquifaction requirement • essentially eliminates latency issue Sustainable Energy Science and Engineering Center Liquid Storage

Requires cryogenic systems

• Equilibrium temperature at 1 bar for liquid hydrogen is ~20 K. • Estimated storage densities1 Berry (1998) 4.4 MJ/liter Dillon (1997) 4.2 MJ/liter Klos (1998) 5.6 MJ/liter • Issues with this approach are: – dormancy. – energy cost of liquifaction.

1 J. Pettersson and O Hjortsberg, KFB-Meddelande 1999:27 Sustainable Energy Science and Engineering Center Gaseous Hydrogen Storage

Hydride storage of hydrogen may be compared to the compression of hydrogen

Higher Heating value of Hydrogen: 142 MJ/kg 1970 1980 1990 2000 2010 2020

Source: The Future of : Bright or Bleak? Baldur Eliasson and Ulf Bossel, ABB Switzerland Ltd. Sustainable Energy Science and Engineering Center Hydrogen Storage - Liquefaction

Total energy requirement for

liquefaction of 1 kg of H2

1970 1980 1990 2000 2010 2020

Source: The Future of Hydrogen Economy: Bright or Bleak? Baldur Eliasson and Ulf Bossel, ABB Switzerland Ltd. Sustainable Energy Science and Engineering Center Hydrogen Delivery - Pipelines

1970 1980 1990 2000 2010 2020

Source: The Future of Hydrogen Economy: Bright or Bleak? Baldur Eliasson and Ulf Bossel, ABB Switzerland Ltd. Sustainable Energy Science and Engineering Center Hydrides

Chemically bond hydrogen in a solid material • This storage approach should have the highest hydrogen packing density. • However, the storage media must meet certain requirements: – reversible hydrogen uptake/release – lightweight with high capacity for hydrogen – rapid kinetic properties – equilibrium properties (P,T) consistent with near ambient conditions. • Two solid state approaches – hydrogen absorption (bulk hydrogen) – hydrogen adsorption (surface hydrogen) including cage structures Sustainable Energy Science and Engineering Center Hydrides Sustainable Energy Science and Engineering Center Alanates Sustainable Energy Science and Engineering Center Complex Hydrides Sustainable Energy Science and Engineering Center Hydrogen Storage Volume Sustainable Energy Science and Engineering Center Hydrogen System Weight Sustainable Energy Science and Engineering Center Future Sustainable Energy Science and Engineering Center US DOE Strategy Sustainable Energy Science and Engineering Center US DOE Strategy Sustainable Energy Science and Engineering Center Complex Hydrides Sustainable Energy Science and Engineering Center Complex Hydrides

Source: Ali T. Raissi, FSEC Sustainable Energy Science and Engineering Center Fuel Tank Problem Sustainable Energy Science and Engineering Center Current Status Sustainable Energy Science and Engineering Center Compressed Gas System Requirements Sustainable Energy Science and Engineering Center Storage System Requirements Sustainable Energy Science and Engineering Center Improvements Sustainable Energy Science and Engineering Center US DOE Targets Sustainable Energy Science and Engineering Center US DOE Strategy Sustainable Energy Science and Engineering Center FCEV Storage System Comparative Volumes and Weights of a FCEV Hydrogen Storage System (Capable of 560 km (350 mi) Range – Compact Sedan)

800 700 600 500 Liters 400 kg 300 Liters kg 200 100 0 ICE Case (Refere24 Comp Liquid H2(< 300 Lm M Sod iq etal Hy 8 uid H2 ( b iu ar H2 re m B ss d e ride (Mg o d H >5 ro 40 h y yd dro mm ri n m ) d ce) g e en dia. d i a (3 ) .) 4 5 ba

r) Sustainable Energy Science and Engineering Center LH2 Tank Configuration

inner vessel super insulation outer vessel level probe filling line suspension gas extraction liquid extraction liquefied hydrogen 253°C) filling port safety valve

gaseous hydrogen (+20°C up to +80°C)

shut off valve

electrical heater cooling water reversing valve heat exchanger (gaseous / liquid) Sustainable Energy Science and Engineering Center Storage Systems

System System Extraction System Fuel Dormancy Safety Weight Volume Complexity Cost Cost

Compressed Gas (5,000 psi)

Cryogenic Liquid H2

Cryo - Liquid Compressed H2

Rechargeable Metal Hydride

Carbon Adsorbtion

Chemical Hydride

Good Acceptable Problem