수소에너지사회 구현을 위한 수소 저장기술

Hydrogen Storage Technology for the Hydrogen Economy

전북대학교/㈜케이시알
이중희

1
 Hydrogen Economy Chain

Storage

Production Conversion Application

Delivery

The hydrogen economy comprises

the production of hydrogen using coal, natural gas, nuclear energy, or
renewable energy
the transport and storage of hydrogen in some fashion
the end use of hydrogen in fuel cells, which combine oxygen with the
hydrogen to produce electricity

2
 What is a Fuel Cell?

Hydrogen

Oxygen

Gas Diffusion Layer Gas Diffusion Layer

Bipolar Plate With Catalyst With Catalyst Bipolar Plate
Membrane
(Anode) (Cathode)

Proton Exchange Membrane (PEM)

Fuel cells combine hydrogen and oxygen electrochemically to produce electricity.

The only by-products are water and useful heat.
3
Fuel Cell Products

Stationary Fuel Cells Residential Fuel Cells

Auxiliary Power Units (APUs)

Micro Fuel Cells

4
Fuel Cell Products

Special Vehicle

Transportation Fuel Cells

5
 Fuel Cell Vehicle

Hydrogen Storage Tank

DaimlerChrysler NECAR-4
Nissan Xterra FCV

Fuel Cell Stack

6
Fuel Cell Vehicle

Toyota FCHV-4
„ Base platform : Kluger V
„ Maximum speed : Over 150
km/h
„ Cruising distance : Over 250 km
„ Hydrogen Storage : Compressed
H2 tank(35MPa)

Hyundai Santa Fe FCEV

„ Base platform : SUV Santa Fe
„ Maximum speed : 124 km/h
„ Cruising distance : 160 km
„ Hydrogen Storage : Compressed
H2 tank(35MPa) Quantum Tech.

7
Fuel Cell Vehicle

Ford Focus FCV

„ Base platform : Compact Focus
„ Maximum speed : 160 km/h
„ Cruising distance : 320 km
„ Hydrogen Storage : Compressed
H2 tank(35MPa) Dynetek

Nissan Xterra FCV

„ Base platform : SUV Xterra
„ Maximum speed : 120 km/h
„ Cruising distance : ?
„ Hydrogen Storage : Compressed
H2 tank(35MPa) Dynetek

8
Fuel Cell Vehicle

GM Opel HydroGen 1
„ Base platform : Opel Zafira
„ Maximum speed : 135 km/h
„ Cruising distance : 400 km
„ Hydrogen Storage : Liquid H2 tank (60L)

DaimlerChrysler NECAR-4
„ Base platform : Mercedes-Benz A-class
„ Maximum speed : 145 km/h
„ Cruising distance : 450 km

„ Hydrogen Storage : Liquid H2 tank

9
 Current DOE Hydrogen
Storage Activity
Technology Organizations Project Focus
Quantum 10,000 psi Composite Tanks
Johns Hopkins University,
Compressed Conformable Tanks
Lincoln Composites
Hydrogen Tanks
Lawrence Livermore National
Lightweight Composite Tanks
Laboratory
Liquid Hydrogen Lawrence Livermore National
Insulated Pressure Vessels
Tanks Laboratory
University of Hawaii Alanates - Kinetics, Mechanisms
Sandia National Laboratory - Alanates - Kinetics, Mechanisms,
Complex Metal
Livermore Engineering
Hydrides
United Technologies Alanates - Cycle Life, System
Research Center Engineering, Safety
National Renewable Energy
Carbon Nanotubes - Kinetics, Mechanism
Laboratory
Standard Test Protocol,
Testing and Evaluation Southwest Research Institute
Independent Test Facility 10
DOE H2 Storage Target

Storage Parameter Units 2005 2010 2015

Weight efficiency kg H2/kg 0.045 0.06 0.09
(Usable specific energy) kW hr/kg (1.5) (2.0) (3.0)
Volumetric efficiency kg H2/L 0.036 0.045 0.081
(Usable energy density) (kW hr/L) (1.2) (1.5) (2.7)
$/kg H2 200 133 67
Storage system cost
($/kW hr) (6) (4) (2)
Cycle life (1/4 tank to full) Cycles 500 1000 1500
Refueling rate kg H2/min 0.5 1.5 2
Loss of useable hydrogen (g/hr)/kg H2 1 0.1 0.05
Federal enclosed-area
Permeation and leakage Scc/hr
safety-standard

11
 Status of H2 Storage System

System Volumetric & System Cost per kWh

Gravimetric Capacity $/kWh
2.7
2015 target 3.0 2015 target $2

1.5
2010 target 2.0 2010 target $4

1.4
Chemical Chemical
1.6 $8
hydride hydride
kWh/L
0.6 Complex
Complex 0.8 kWh/kg
hydride $16
hydride
1.6
Liq. H2 2.0 Liq. H2 $6

1.3
700 bar 1.9 700 bar $16

0.8
350 bar 2.1 350 bar $12

0 1 2 3 4 0 5 10 15 20
$/kWh
12
Hydrogen Storage Method

Compressed H2 gas

Cryogenic liquid H2

H2 adsorbed on activated metal hydrides

H2 adsorbed on activated carbon nanotubes

13
 Hydrogen Station

Metal hydride H2 storage 14

Comparison with
Hydrogen Storage Method

200

Diesel

100
Volumetric Density (kg/m )

3 Gasoline
80
DOE Target
60 Low Temperature
Chemical Storage
Metal Hydride
(NaBH4)
40
Liquid Hydrogen

High Temperature
Metal Hydride
20

Compressed Hydrogen

10

6
1 2 4 6 8 10 20

Gravimetric Density (% weight H2)

15
Compressed H2 Storage

Advantage
„ Simplicity of design and use

„ High storage mass fraction

„ Rapid refueling capability

„ Excellent dormancy characteristics

„ Minimal infrastructure impact

„ High safety due to the inherent strength of the pressure vessel

„ Little to no development risk

Disadvantage
„ System volume

16
History of Compressed Gas Tank

Compressed Gases Have Been Around for Over 100 Years

17
 Types of Gas Storage Tank

Type 1
„ All Metal (steel, aluminum, etc.)

Type 2
„ Metal liner reinforced with resin impregnated continuous filament
(hoop wrapped)
Type 3
„ Metal liner reinforced with resin impregnated continuous filament
(full wrapped)
Type 4
„ Resin impregnated continuous filament with a non-metallic liner (all
composites)

18
 Storage Efficiency of
Compressed Gas Tank
H2 Mass Storage Efficiency (wt%)

12

2015 DOE Target

(9wt%)

2010 DOE Target

(6wt%)

6 “Type 4” All-Composites

“Type 3” Full-Wrapped
3 Aluminum
“Type 1” Steel Tanks

“Type 2” Hoop-Wrapped

Prior to1980 1980 1990 2000 2010 2015

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Compressed H2 Tank (Type3)

Seamless Thin Wall Aluminum Liner

„ Increased storage capacity with
the thin wall liner
„ Non-permeable
„ Resistance to corrosion and impact

„ High Strength Carbon &

Toughened Epoxy Overwrap
„ Maximizes strength to weight ratios
„ Resistant to : UV rays, acids, oils, salt,
cleaning agents, and water

DyneCell™ Hydrogen Tank

of Dynetek Industries Ltd.
20
 Compressed H2 Tank(Type4)

„ Polymer Liner
„ Unibody polymer construction
„ Reliable, redundant double seal system
„ Minimized leak-paths : 1-boss liner system

Carbon/Epoxy Overwrap
Carbon fiber resists corrosion
„
and fatigue damage
„ Burst pressure is 100%
supported and sustained over
service-life by carbon fiber
„ Impact Resistant External Shell
„ Increased safety margin
„ Proprietary fiber/resin system yields
superior damage protection

TriShield™ Hydrogen Storage Tank of QUANTUM Tech. 21

 Compressed H2 Tank(Type4)

Typical GDATP Roof Pack Storage System

GDATP All-Composite Hydrogen Storage Tank

GDATP-JHU/APL Integrated Storage System
TUFFSHELL™ All-Composite Fuel Tank of GDATP Lincoln Operation
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Compressed H2 Tank(Type4)

Composite wrapped tank

prototype using thin-wall liner

Lawrence Livermore National

Laboratory, IMPCO Technologies
and Thiokol Propulsion

Permeation reduction coatings

~12% hydrogen by weight

5000 psi [34.5 MPa] service, 300

K, safety factor 2.25

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 Composite Tank(Type4) (KCR)

Composite Tank of KCR

Korea Patent Pending : 10-2001-0071708
PE/Clay Nanocomposite Liner

Thermosetting Adhesives

Acid-treatment Surface
Carbon Fiber
Plasma treatment Composite Shell
Impact Damage
Aluminum End Nozzle Resistance Form

Glass Fiber
Composite Shell

Aluminum End Nozzle PE/Clay Nanocomposite Liner

• Korea Patent No. 20-031502 • Korea Patent No.10-0412048
• Korea Patent Pending
: 10-2004-0016341 24
 Conformable H2 Tank

„ Storage Pressure : 5,000 psig

„ Water volume : 68 liters
„ External dimensions :
approx. 12.8 in. x 21.2 in. x 27.9 in.
„ Providing 23% more capacity than
two cylinders in the same volume
envelope.

Thiokol Propulsion H2 Tank

25
 Integrated Storage System

GDATP-JHU/APL Integrated Storage System (ISS)

CHISS Demonstration
Property
Pressure Cell Tank
Operating Pressure 350 bar 700 bar
Diameter 304 mm 434 mm
Length 1067 mm 1308 mm
Weight 19 kg 81 kg
Empty Volume 59 L 111 L
CH2 Capacity 1.40 kg 4.4 kg
Rupture Pressure 900 bar 1750 bar

Several smaller tanks can be used to create a fuel system package that conforms to a
non-cylindrical cavity, such as a traditional gasoline fuel tank compartment.

26
 Comparison of Tank PF

2,500,000 PF=Tank Performance Factor

Tank Structure Performance Factor (Inches)

=Operating Pressure X Safety Factor X Internal Volume / Tank Weight

2,000,000

1,500,000 T1000G

1,000,000 T700

500,000

0
Steel Aluminum Titanium E-Glass/ S-Glass/ Aramid/ Carbon/ Carbon/ Carbon/
Aluminum Aluminum Aluminum Aluminum Plastic Metalized
Liner Liner Liner Liner Liner Polymer
Liner
Comparison of tank performance factor
for various materials/technologies 27
 Weight & Volume Impact of
Storage Pressure

700 7000
Tank Performance Factor = 1.3 million inches
600 Tank Safety Factor = 2.25 6000
Gas Temperature = 300K

Internal Volume (L)

Tank hold 6.8 kg of H2
Tank Mass (kg)

500 5000

400 4000

300 3000
Mass (Kg)
200 Volume (L) 2000

100 1000

0 0
0.00 20.00 40.00 60.00 80.00 100.00

Pressure (MPa)
28
 Volumetric Density of
Compressed H2 Gas

H2liq
Volumetric H2 density (kg/m3)

0.25

60
0.20
H2gas
Ideal gas

dw / do
40 0.15

0.10
σv = 460 MPa (steel)
20
0.05

0 0.00
0 50 100 150 200
Pressure (MPa)
29
 Liquid H2 Storage

Advantage
„ One of the highest H2 mass fractions

„ One of the lowest system volumes

„ Near zero development risk

„ Good fast fill capability

„ Acceptable safety characteristics

Disadvantage
„ Dormancy concerns arise due to boil-off losses
„ The liquefaction process is costly
„ Small scale liquid hydrogen production is impractical

30
Liquid H2 Storage Tank

31
 Fuel Cell Bus for Berlin,
Copenhagen, Lisbon

Vehicle Type Length, weight (max.): MAN Nutzfahrzeuge AG Low floor bus 12 m, 18 ton
Basic bus: NL A21, diesel-electric
Propulsion system: Central drive unit (Siemens): 2 x 75 kW, summation gearbox
LH2-storage: Linde: 600 liter LH2, -253°C
Electric storage system (phase 2): 60kW, 25kWh; battery/super capacitors (tbd)
Fuel cell stacks power output (net): 75 kW

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Liquid H2 Storage Tank

The Linde vehicle tank with a

cylindrical cross-section has the
following characteristics:
Storage medium: LH2
External tank dimensions:
„ Diameter: 500 mm
„ Entire length incl. support: Approx.
5,500 mm
Geometrical internal tank volume:
approx. 600 liter
Filling volume (approx. 90% of the
geometrical internal volume): Approx.
540 liter
Operational pressure of the internal
container: 0~8 bar
Design temperature: 20 K ~ 353 K
33
 Metal Hydride H2 Storage

Advantages
„ Fairly dense H2 storage

„ Good safety characteristics

Disadvantages
„ Bad characteristics of dissociation (high temperature, high energy
input)
„ Very much too heavy

„ Operating requirements are poorly matched to PEM FCV

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 Solid H2 Storage System

Atomic Hydrogen chemically bonded to the solid and released by heat

M + H2 ' MH + U H

H H
H H

Design Requirements:
• Suitable MH Alloy
• Efficient Heat Exchanger
• Light Weight Vessel
35
 Solid H2 Storage Tank

Volume : 60 liters,
Stored hydrogen : 3 kg H2
@ 1,500 psi
System weight : 190 kg
Cruising distance : 240 km
Texaco Ovonic Hydrogen Systems

Ovonic Onboard Vessel Compressed H2 Vessel

Stored hydrogen : 3 Kg H2 Stored hydrogen : 0.78 Kg H2

@ 1,500 psi @ 5,000 psi
Cruising distance : 64 km
Cruising distance : 240 km

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 Solid H2 Storage System for
Hybrid Vehicle

Special Features
„ Reversible
„ Safe
„ Compact
„ Low pressure operation
„ Cold temperature start-up
„ Packing flexibility
„ Onboard waste heat for
desorption

2002 Ovonic Hydrogen Prius

37
 Solid H2 Storage System
for Hybrid Vehicle
ICE with
OvonicTM Modification
Texaco Ovonic Hydrogen Systems
OvonicTM Soid Hydrogen Storage
Hydrogen Sensor
OvonicTM Solid
Hydrogen Storage Tank Expansion Tank

Coolant Pump
ICE Coolant Solenoid Valve
Supply/Return
Heat
Exchange

Drive Train Electric Motor OvonicTM NiMH Battery

System Technology

Ovonic technology enables an all-hydrogen ICE vehicle

38
 H2 Storage in Carbon Nanotube

Simulation of the interaction between

Representation of the carbon nanotube structures nanotubes (20,0) and hydrogen

39
H2 Storage in Nanotube

Hydrogen

Nanotube

Scrolled nanotube Scrolled nanotube bundle

40
H2 Storage in MOFs

Highly porous metal-organic frameworks

(synthesized by Yaghi's group in 2001)

41
 Conclusions

Automobile manufacturers in USA, Japan, and Korea has a

trend to prefer compressed H2 gas storage system
European countries prefer liquid H2 storage system
Hydrogen storage technology is very important to realize
Hydrogen Economy
Balanced technical developments in various storage methods
are needed at the current situation
The hydrogen storage technology is one of the key technologies
for Hydrogen Economy

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감사합니다

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