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수소에너지사회 구현을 위한 수소 저장기술

Hydrogen Storage Technology for the Hydrogen Economy

전북대학교/㈜케이시알

이 중 희

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Hydrogen Economy Chain

Production

Delivery

Storage

Conversion Application

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

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What is a Fuel Cell?

Hydrogen

Oxygen

Gas Diffusion LayerWith Catalyst

Gas Diffusion LayerWith Catalyst MembraneBipolar Plate

(Anode)Bipolar Plate

(Cathode)

Proton Exchange Membrane (PEM)

Fuel cells combine hydrogen and oxygen electrochemically to produce electricity. The only by-products are water and useful heat.

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Fuel Cell Products

Stationary Fuel Cells Residential Fuel Cells

Auxiliary Power Units (APUs)

Micro Fuel Cells

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Fuel Cell Products

Special Vehicle

Transportation Fuel Cells

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Fuel Cell Vehicle

Fuel Cell Stack

DaimlerChrysler NECAR-4Nissan Xterra FCV

Hydrogen Storage Tank

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

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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

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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-4Base platform : Mercedes-Benz A-class Maximum speed : 145 km/h Cruising distance : 450 kmHydrogen Storage : Liquid H2 tank

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Current DOE Hydrogen Storage Activity

Technology Organizations Project FocusQuantum 10,000 psi Composite TanksJohns Hopkins University, Lincoln Composites Conformable TanksCompressed

Hydrogen TanksLawrence Livermore National Laboratory Lightweight Composite Tanks

University of Hawaii Alanates - Kinetics, Mechanisms

United Technologies Research Center

Alanates - Cycle Life, System Engineering, Safety

Testing and Evaluation Southwest Research Institute Standard Test Protocol, Independent Test Facility

Complex Metal Hydrides

Liquid Hydrogen Tanks

Lawrence Livermore National Laboratory Insulated Pressure Vessels

Sandia National Laboratory -Livermore

Alanates - Kinetics, Mechanisms, Engineering

Carbon National Renewable Energy Laboratory Nanotubes - Kinetics, Mechanism

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DOE H2 Storage Target

Storage Parameter Units 2005 2010 2015

Weight efficiency(Usable specific energy)

kg H2/kgkW hr/kg

0.045(1.5)

0.06(2.0)

0.09(3.0)

Storage system cost $/kg H2($/kW hr)

200(6)

133(4)

67(2)

Refueling rate kg H2/min 0.5 1.5 2

Permeation and leakage Scc/hr Federal enclosed-area safety-standard

Volumetric efficiency(Usable energy density)

kg H2/L(kW hr/L)

0.036(1.2)

0.045(1.5)

0.081(2.7)

Cycle life (1/4 tank to full) Cycles 500 1000 1500

Loss of useable hydrogen (g/hr)/kg H2 1 0.1 0.05

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Status of H2 Storage System

System Volumetric & Gravimetric Capacity

2.73.0

1.52.0

1.41.6

0.60.8

1.62.0

1.31.9

0.82.1

kWh/LkWh/kg

2015 target

2010 target

Chemical hydride

Complex hydride

Liq. H2

700 bar

350 bar

System Cost per kWh$/kWh

$2

$4

$8

$16

$16

$6

$12

2015 target

2010 target

Chemical hydride

Complex hydride

Liq. H2

700 bar

350 bar

0 5 10 15 20$/kWh

0 1 2 3 4

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Hydrogen Storage Method

Compressed H2 gas

Cryogenic liquid H2

H2 adsorbed on activated metal hydrides

H2 adsorbed on activated carbon nanotubes

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Hydrogen Station

Metal hydride H2 storage

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Comparison with Hydrogen Storage Method

Low TemperatureMetal Hydride

Compressed Hydrogen

High TemperatureMetal Hydride

Liquid Hydrogen

DOE TargetGasoline

Diesel

6

8

10

20

40

60

80

100

200

1 2 4 6 8 10 20

Chemical Storage(NaBH4)

Volu

met

ric D

ensi

ty (k

g/m

3 )

Gravimetric Density (% weight H2)

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Compressed H2 Storage

Advantage Simplicity of design and useHigh storage mass fractionRapid refueling capabilityExcellent dormancy characteristicsMinimal infrastructure impactHigh safety due to the inherent strength of the pressure vesselLittle to no development risk

DisadvantageSystem volume

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History of Compressed Gas Tank

Compressed Gases Have Been Around for Over 100 Years

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Types of Gas Storage Tank

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

Type 2Metal liner reinforced with resin impregnated continuous filament (hoop wrapped)

Type 3Metal liner reinforced with resin impregnated continuous filament (full wrapped)

Type 4Resin impregnated continuous filament with a non-metallic liner (all composites)

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Storage Efficiency of Compressed Gas TankH

2M

ass

Stor

age

Effic

ienc

y (w

t%)

1980 1990 2000 2010Prior to1980

“Type 1” Steel Tanks

“Type 2” Hoop-Wrapped

“Type 3” Full-Wrapped Aluminum

“Type 4” All-Composites

3

6

9

12

2015

2010 DOE Target (6wt%)

2015 DOE Target (9wt%)

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Compressed H2 Tank (Type3)

High Strength Carbon & Toughened Epoxy Overwrap

Maximizes strength to weight ratiosResistant to : UV rays, acids, oils, salt, cleaning agents, and water

Seamless Thin Wall Aluminum LinerIncreased storage capacity with the thin wall linerNon-permeableResistance to corrosion and impact

DyneCell™ Hydrogen Tank of Dynetek Industries Ltd.

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Compressed H2 Tank(Type4)

Polymer LinerUnibody polymer constructionReliable, redundant double seal systemMinimized leak-paths : 1-boss liner system

TriShield™ Hydrogen Storage Tank of QUANTUM Tech.

Carbon/Epoxy OverwrapCarbon fiber resists corrosion and fatigue damageBurst pressure is 100% supported and sustained over service-life by carbon fiber

Impact Resistant External ShellIncreased safety marginProprietary fiber/resin system yields superior damage protection

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Compressed H2 Tank(Type4)

TUFFSHELL™ All-Composite Fuel Tank of GDATP Lincoln Operation

Typical GDATP Roof Pack Storage System

GDATP-JHU/APL Integrated Storage System GDATP All-Composite Hydrogen Storage Tank

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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

PE/Clay Nanocomposite Liner• Korea Patent No.10-0412048

Impact Damage Resistance Form

Carbon FiberComposite Shell

Aluminum End Nozzle• Korea Patent No. 20-031502• Korea Patent Pending

: 10-2004-0016341

Acid-treatment Surface

PE/Clay Nanocomposite Liner

Aluminum End Nozzle

Korea Patent Pending : 10-2001-0071708

Glass FiberComposite Shell

Thermosetting Adhesives

Plasma treatment

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Conformable H2 Tank

Storage Pressure : 5,000 psigWater volume : 68 litersExternal 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

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Integrated Storage System

GDATP-JHU/APL Integrated Storage System (ISS)

Property CHISS Pressure Cell

Demonstration Tank

Operating Pressure 350 bar 700 bar

Length 1067 mm 1308 mm

Empty Volume 59 L 111 L

Rupture Pressure 900 bar 1750 bar

Diameter 304 mm 434 mm

Weight 19 kg 81 kg

CH2 Capacity 1.40 kg 4.4 kg

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.

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Comparison of Tank PF

Comparison of tank performance factor for various materials/technologies

0

500,000

1,000,000

1,500,000

2,000,000

2,500,000

Tank

Str

uctu

re P

erfo

rman

ce F

acto

r (In

ches

)

Steel Aluminum Titanium E-Glass/Aluminum

Liner

S-Glass/Aluminum

Liner

Aramid/Aluminum

Liner

Carbon/Aluminum

Liner

Carbon/PlasticLiner

Carbon/MetalizedPolymer

Liner

T1000G

T700

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

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Weight & Volume Impact of Storage Pressure

Tank

Mas

s (k

g)

Tank Performance Factor = 1.3 million inchesTank Safety Factor = 2.25Gas Temperature = 300KTank hold 6.8 kg of H2

0.00 20.00 60.00 100.0040.00 80.000

700

600

500

400

300

200

100

0

7000

6000

5000

4000

3000

2000

1000

Mass (Kg)Volume (L)

Internal Volume (L)

Pressure (MPa)

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Volumetric Density of Compressed H2 Gas

0 50 100 150 200

Pressure (MPa)

60

40

20

0

0.25

0.20

0.15

0.10

0.05

0.00

H2liq

H2gas

Ideal gas

σv = 460 MPa (steel)

Volu

met

ric H

2de

nsity

(kg/

m3 )

dw / d

o

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Liquid H2 Storage

AdvantageOne of the highest H2 mass fractions One of the lowest system volumesNear zero development riskGood fast fill capabilityAcceptable safety characteristics

DisadvantageDormancy concerns arise due to boil-off losses The liquefaction process is costly

Small scale liquid hydrogen production is impractical

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Liquid H2 Storage Tank

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Fuel Cell Bus for Berlin, Copenhagen, Lisbon

Vehicle Type Length, weight (max.): MAN Nutzfahrzeuge AG Low floor bus 12 m, 18 tonBasic bus: NL A21, diesel-electricPropulsion system: Central drive unit (Siemens): 2 x 75 kW, summation gearboxLH2-storage: Linde: 600 liter LH2, -253°CElectric 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

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Metal Hydride H2 Storage

AdvantagesFairly dense H2 storage Good safety characteristics

DisadvantagesBad 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 + H

H

H

H

H

Design Requirements:• Suitable MH Alloy• Efficient Heat Exchanger• Light Weight Vessel

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Solid H2 Storage Tank

Texaco Ovonic Hydrogen Systems

Volume : 60 liters, Stored hydrogen : 3 kg H2@ 1,500 psiSystem weight : 190 kgCruising distance : 240 km

Ovonic Onboard Vessel

Stored hydrogen : 3 Kg H2@ 1,500 psi

Cruising distance : 240 km

Compressed H2 Vessel

Stored hydrogen : 0.78 Kg H2 @ 5,000 psi

Cruising distance : 64 km

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Solid H2 Storage System for Hybrid Vehicle

2002 Ovonic Hydrogen Prius

Special FeaturesReversibleSafeCompactLow pressure operationCold temperature start-upPacking flexibilityOnboard waste heat fordesorption

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Solid H2 Storage Systemfor Hybrid Vehicle

Drive Train Electric Motor OvonicTM NiMH BatterySystem Technology

ICE withOvonicTM Modification

Texaco Ovonic Hydrogen SystemsOvonicTM Soid Hydrogen Storage

ICE CoolantSupply/Return

OvonicTM SolidHydrogen Storage Tank

Hydrogen Sensor

Expansion Tank

Coolant Pump

Solenoid Valve

Heat Exchange

Ovonic technology enables an all-hydrogen ICE vehicle

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H2 Storage in Carbon Nanotube

Representation of the carbon nanotube structuresSimulation of the interaction between

nanotubes (20,0) and hydrogen

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H2 Storage in Nanotube

Hydrogen

Nanotube

Scrolled nanotube Scrolled nanotube bundle

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H2 Storage in MOFs

Highly porous metal-organic frameworks(synthesized by Yaghi's group in 2001)

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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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