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Thermodynamics Aspects of Hydrogen Storage in Metals Guy Joël Rocher Mech 6661 December 5 th , 2011

Thermodynamics Aspects of Hydrogen Storage in Metals

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Page 1: Thermodynamics Aspects of Hydrogen Storage in Metals

Thermodynamics Aspects of

Hydrogen Storage in Metals

Guy Joël Rocher

Mech 6661

December 5th , 2011

Page 2: Thermodynamics Aspects of Hydrogen Storage in Metals

Outline

• Introduction

• Thermodynamics of H2 Fuel Cells

• Thermodynamics of H2 storage

• Concluding Remarks

2

Page 3: Thermodynamics Aspects of Hydrogen Storage in Metals

3

1.

Introduction

Page 4: Thermodynamics Aspects of Hydrogen Storage in Metals

Introduction

• Why Hydrogen Energy?1. Reduction in GHG emission

2. Reduction of oil dependency

3. Energy efficiency increase (conv. 20% elec. 45%)

• What is Hydrogen Energy? H2 is an Ultra High performance battery (Energy carrier)

Hydrogen = Electrification

• When? 2015 100 000 electric cars target in Europe

4

Palcan Energy, Canada

A. Lulianelli, A. Basile, Catal. Sci. Technol., 2011

Page 5: Thermodynamics Aspects of Hydrogen Storage in Metals

Canadian Interest in H2

• 18,608,297 cars in 2005 Canada (620/1000)

5

Natural Resources Canada 2011

Environment Canada, 2011Environment Canada, 2011

Page 6: Thermodynamics Aspects of Hydrogen Storage in Metals

• HEV: Hybrid Electric Vehicle

ICE + Battery

• PHEV: Plug In Hybrid Electric Vehicle

Large Battery

• FCEV: Fuel Cell Electric Vehicle

H2 Tank + Fuel Cell + Small Battery

Electric Vehicles Classification (EV)

6

Electric Motor + 3-50KW

+ Electric Motor 100+KW

Electric Motor 75 KW Images: SAE Presentation, Dr. James Gover, Kettering University

Page 7: Thermodynamics Aspects of Hydrogen Storage in Metals

H2 Powered Vehicles (FCEV)

• 2011 Honda FCX Clarity200 units, Southern California, 600$/month 3year term.

7

http://automobiles.honda.com/fcx-clarity/

Page 8: Thermodynamics Aspects of Hydrogen Storage in Metals

8

2.

Thermodynamics of Fuel Cells

Page 9: Thermodynamics Aspects of Hydrogen Storage in Metals

Electrochemical Cell “Engine”

• Open System with Mass Flow, Work and Heat

Classical Thermodynamics crucial for design & control of the system.

9

1st Law of Thermodynamics

ΔU = Q – W

ΔU = Internal Energy

Q = Heat Added

W = Work Done

Chemical reactions: Operating Conditions, Material development, etc.

http://www.alternative-energy-news.info/technology/fuel-cells/

Page 10: Thermodynamics Aspects of Hydrogen Storage in Metals

• At system level: Irreversible conversions

Chemical E. Electrical E. Mechanical E.

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Gerry Nolan, Silicon Chip, Issue 166, July 6 2002

Fuel Cells Operation

2nd Law of Thermodynamics

dS ≥ δq/T

S = Entropy

δq = Heat Added

T = Temperature

Operating Conditions, Material development, etc.

Page 11: Thermodynamics Aspects of Hydrogen Storage in Metals

11

3.

Thermodynamics of H2 Storage

Page 12: Thermodynamics Aspects of Hydrogen Storage in Metals

• Compressed Gas

• Liquid H2

• Adsorption

• Metal/Complex Hydrides

• Chemical Reactions

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Thermodynamics of H2 Storage

Internal Energy Change

Phase Change

Weak Physical Bonding

Chemical Bonding

Product Generation

Page 13: Thermodynamics Aspects of Hydrogen Storage in Metals

0

5

10

15

20

25

0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040

Pr

es

su

re

(b

ar

)

Mass Fraction H/(Mg+Ni+H)

PCI Mg67Ni33 + H2350-5

325-4

300-3

Metal hydrides Theory

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AbsorptionDissociation

Page 14: Thermodynamics Aspects of Hydrogen Storage in Metals

0

5

10

15

20

25

0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040

Pr

es

su

re

(b

ar

)

Mass Fraction H/(Mg+Ni+H)

PCI Mg67Ni33 + H2350-5

325-4

300-3

Thermodynamic Modelling

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AbsorptionDissociation

Page 15: Thermodynamics Aspects of Hydrogen Storage in Metals

15

Material Matters, Volume 6, Article 2, 2011

A compilation of the Van’t Hoff plots of selected elemental, classical, and complex hydrides.

Thermodynamics Analysis Tools

The Van’t Hoff plot derived from the isotherms at various temperatures.

Nature 414, 353-358, 2001

ln(eq/eq0) = (-H/R)(1/T) + S/R

The Van’t Hoff equation

-H/R

Page 16: Thermodynamics Aspects of Hydrogen Storage in Metals

• Why? Experimental investigation time consuming

• Models:• Liquid Quasi-Chemical

• Solid Solution Sublattice with random substitution

• Experiments provide:

• ΔHhydride, Solubility range, etc.

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Thermodynamic Modelling

Page 17: Thermodynamics Aspects of Hydrogen Storage in Metals

gas + (Mg) + (Mg2Ni)

(Mg) + (Mg2Ni) + MgH2

(Mg2Ni) + MgH

2 + Mg

2NiH

4

gas + MgH2 + Mg2NiH4356 C

327 C

302 C

22% Mg + 78% Ni -H

Mass fraction, H

log

P (

ba

r)

0 0.01 0.02 0.03 0.04 0.05 0.06

-0.5

0

0.5

1

1.5

2

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Modelling vs Experimental data

Buchner ,1978

Page 18: Thermodynamics Aspects of Hydrogen Storage in Metals

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4.

Concluding Remarks

Page 19: Thermodynamics Aspects of Hydrogen Storage in Metals

Concluding Remarks

• Classical & Statistical Thermodynamics essential for Hydrogen technologies .

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• Thermodynamic Modelling with key experiment allows to faster investigation.

• Renewable & Sustainable Energy?

• Multidisciplinary investigations linked through thermodynamics laws.

Page 20: Thermodynamics Aspects of Hydrogen Storage in Metals

? ¿ Questions ¿?

THANK YOU

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