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CONTENTS 1) Properties of Hydrogen 2) H2 Interactions with materials 3) Hydrogen cycle 4) Applications and safety

HYDROGEN IN MATERIALS: FUNDAMENTALS AND APPLICATIONS Andreas Züttel

Andreas Züttel, Switzerland, 17.07.14 2

ALCHEMY 16th CENTURY


LAVOISIER

Antoine Laurent Lavoisier (1743 - 1794)

Naming Hydrogen correctly according to its origin.

Sir Théodore Turquet de Mayerne (1573 – 1654) was a Swiss-born physician who treated kings of France and England and advanced the theories of Paracelsus.

At 13:45 on December 1, 1783, Jardin des Tuileries in Paris, 1st manned spherical balloon of 4 m diameter

Jacques Alexandre Cesar Charles (1746 - 1823)

CHEMICAL HYDRIDES

Fe + H2SO4 FeSO4 +H2

Ref.: Encyclopædia Britannica


HYDROGEN ISOTOPES

H D T


PROPERTIES OF HYDROGEN

H2 Van der Waals b(H2) = 2.661·10-5 m3·mol-1 V(H2) = 26.6 cm3·mol-1 r(H2) = 2.34 Å

Density of liquid ρ(H2) = 70.8 kg m-3 V(H2) = 28.3 cm3·mol-1 r(H2) = 2.38 Å

r(H0) = 0.37 Å

H0

H-

H+

H

r(H-) = 2.08 Å r(H+) = 10-5 Å


STATES OF HYDROGEN

H0 + e- → H-

H0 → H+ + e-

2 H0 → H2

E / eV

H2 → H+ + H-

-0.75

-4.52

+13.60

+17.37

ΔEdis

ΔEI

0.0

10.0

20.0

H0

Ref.: Wojciech Grochala and Peter P. Edwards, Chem. Rev. 104 (2004), pp. 1283-1315

ΔEA

8

THERMODYNAMIC PROPERTIES OF HYDROGEN

T = 273.15 K p = 1.013 bar = 0.1013 Mpa lower heating 10'800 kJ·m-3 value: 120'000 kJ·kg-1

33.33 kWh ·kg-1 higher heating 12'770 kJ·m-3 value: 141'890 kJ·kg-1

39.41 kWh ·kg-1 gas constant: 4125 J·kg-1 ·K-1 cp at 293 K: 14'266 J·kg-1 ·K-1 Density (gas): 0.08988 kg·m-3 Density (liquid): 70.779 kg·m-3 Density (solid): 86.503 kg·m-3

critical point: Tc: 33.25 K kJ·m-3 pc: 13.07 · 105 Pa phase transition: bp: 20.28 K mp: 14.1 K ΔHv: 451.9 kJ·kg-1 ΔHm: 58.6 kJ·kg-1 vapor pressure [atm] for T < 29 K A1: 2.000620 A2: -50.09708 A3: 1.0044 A4: 0.01748495 for T > 29 K A5: 1.317 ·10-3 A6: -5.926 ·10-5 A7: 3.913 ·10-6

TAAT

AA)plog( 43

21a ⋅+++=

( )

( ) ( )775

6

35a

29TA29TA

29TApp

−+−+

−+=


PRIMITIVE PHASEDIAGRAM OF HYDROGEN

Ref: W. B. Leung, N. H. March and H. Motz, Physics Letters 56A (6) (1976), pp. 425-426

RT


MOLECULAR HYDROGEN

2

2

Vna

bnVTRn)V(p ⋅−⋅−

⋅⋅=


MOLECULAR HYDROGEN

2

2

Vna

bnVTRn)V(p ⋅−⋅−⋅⋅

=

R = 8.314 J·K-1·mol-1 a(H2) = 2.476·10-2 m6·Pa·mol-2 b(H2) = 2.661·10-5 m3·mol-1

HYDROGEN AND SOLIDS

Hydrogen gas Physisorption

Metalhydride

Liquid hydrogen

Complex hydrides Chemical hydrides

AProj.

AProj.

st sl

sr Dp

Dp Dp

da di

dw

casing hemisphere

round suture length suture

hemisphere

a)

b) c) d)


PRESSUR CYLINDER

Ref.: Wilhelm Matek, Dieter Muhs, Herbert Wittel and Manfred Becker, Roloff/Matek Maschinenelemente , Viewegs Fachbücher der Technik, , (1994), 690 pages, ISBN: 3-528-74028-0

PRESSURIZED HYDROGEN STORAGE Hydrogen gas

pp

dd

va

w

Δ+⋅

Δ=

σ2

da di

dw

2

2

)(Vna

bnVTRnVp ⋅−⋅−

⋅⋅=

Material Density Tensile breaking [kg m-3] stress [GPa]

Aluminium Alu 6061-T4 2700 0.145 AISI 4140 Steel 7850 1.650 Spider silk (protein) 1300 1.3 Kevlar (polyaramid) 1440 2.76 Basic Carbon Fiber Composite 1570 0.2 Hexcel® Carbon Fiber AS4D (12,000 Filaments) 1790 4.280

Ref.: F. Vollrath & D. P. Knight, NATURE 410 (2001), pp. 541-549

R = 8.314 J·K-1·mol-1 a(H2) = 2.476·10-2 m6·Pa·mol-2, b(H2) = 2.661·10-5 m3·mol-1


HYDROGEN STORAGE DENSITY

Dynatek

HYDROGEN STORAGE VESSELS

Ref: Dynetek Europe GmbH, Breitscheider Weg 117a, D-40885 Ratingen, URL: http://www.dynetek.de


LIQUID HYDROGEN

Plant for liquefying hydrogen (Linde)

Claude process for liquefying hydrogen

Energy use for liquefaction: Wth = 3.92 kWh·kg-1 Wprac = 10 kWh·kg-1

75% Orthohydrogen at RT 25% Parahydrogen

ΔH(T


PARA- UND ORTHO HYDROGEN

HYDROGEN STORAGE Liquid hydrogen 75% Orthohydrogen

at RT 25% Parahydrogen

ΔHvap(T=21.2K) 452 kJ·kg-1

ΔH(T

0

50

100

150

200

0 10 20 30

Hy

dro

ge

n d

en

sit

y [

kg

/m3]

Hydrogen density [kg H2/ 100kg storage material] Andreas Züttel, Switzerland, 17.07.14

HYDROGEN DENSITY

carbon hydrates liq. hydro-

carbons

comp. H2 gas

liq. H2

liq. natural gas

NH3


LENNARD-JONES POTENTIAL

!!"

#

$$%

&'(

)*+

, σ−'(

)*+

, σ⋅ε⋅=612

rr4)r(V

-ε σ = collision distance ε = binding energy

r = σ

r0 = 21/6 σ

Van der Waals interaction

Pauli repulsion dipole

Andreas Züttel, University of Fribourg, 17.07.14

INTERACTION OF GASES WITH SURFACES

Adsorption Desorption

Monolayer Multilayer

GASPHASE

ADSORBAT

ADSORBER

SURFACE OF A SOLID

Andreas Züttel, Switzerland, 17.07.14

ADSORPTIONS ISOTHERMEN

PHYSISORPTION

( ) ( )( )β⋅−+⋅β−β⋅

=111 c

cnn

m

TkHH Vads

ec ⋅Δ−Δ

=00

0

ppe

kkF Tk

H

d

aV

=⋅=β ⋅Δ

el. chem. at 298K

gas phase at 77 K

theoretical calculation 32 K

Ref.: A. Züttel et al., Int. J. of Hydrogen Energy 27 (2002), pp. 203-212 M.G. Nijkamp et al., Appl. Phys. A 72 (2001), pp. 619–623 S. Brunauer, P. H. Emmett und E. Teller, J. Amer. Chem. Soc. 60 (1938), p. 309

PHYSISORPTION

Ref.: Maurice Schlichtenmayer and Michael Hirscher, „Nanosponges for hydrogen storage“, J. Mater. Chem., 22 (2012), 10134

ρ =1

1ρm

+ Aspec ⋅δ


SINGLE WALL CARBON NANOTUBE (5,5)

6.8 Å H2

RNT

Rads

r

R

ΔHV

ΔHads

ΔHads dads

CHEMICAL HYDRIDES

Ref: A. Züttel, Materials for hydrogen storage , materialstoday, Septemper (2003), pp. 18-27 http://www.youtube.com/watch?v=uixxJtJPVXk

Al + 3 H2O → Al(OH)3 + 1½ H2 5.6 mass%

NaAlH4 + 4 H2O → NaOH + Al(OH)3+ 4 H2 14.8 mass% NaBH4 + 3 H2O → NaOH + HBO2+ 4 H2 21.3 mass%

LiBH4 + 3 H2O → LiOH + HBO2+ 4 H2 37.0 mass%

NaBH4 + 4 H2O → NaOH + HBO3+ 5 H2 35.7 mass%

LiBH4 + 4 H2O → LiOH + HBO3+ 5 H2 45.5 mass%

M + x H2O → M(OH)x + x/2 H2 x/2 H2 + x/4 O2 → x/2 H2O

OXIDATION VON METALLEN MIT WASSER

CHEMICAL HYDRIDES

ΔHf0 -419 kJ

ΔHf0 +848 kJ ΔHf0

-429 kJ

HYDROGEN CYCLE

SUN

ENERGY

ELECTROLYSIS

ENERGY

COMBUSTION

39 kWh/kg

2 H2O → 2 H2 + O2

STORAGE M + ½H2 → MH

82%

25% 85%

50%

CLOSED CYCLE!

WATER DISSOCIATION H2O → H2 + ½ O2

-300

-250

-200

-150

-100

-50

0

0 500 1000 1500 2000 2500 3000Temperature [K]

Ene

rgy

[kJ]

T·ΔSd

ΔGd

ΔHd

ΔQ

ΔW

H2O

H2 , O2

ΔH

HYDROGEN PRODUCTION FROM RENEWABLE ENERGY

ELECTROLYSIS 8 MW, 85% efficiency

SOLAR CONCENTRATOR Zn-cycle, HT-Turbine

PHOTO-ELECTROLYSIS Grätzel cell

BIOMASS CONVERSION Methane

LARGE SCALE ELECTROLYSER

Technical data: Voltage: 1.48 V (1.85 V) Energy: 39.4 kWh/kg H2 (49 kWh/kg H2) (1 kg H2 = 11.2 m3 H2 at 1 bar) Efficiency: >80%

High pressure electrolyser (30 bar), 40‘000 Nm3H2 per day (8 MW), Lurgi, Giovanola (Monthey, Switzerland)


ENERGY CONVERSION DEVICES

Steam engine

Steam turbine

Internal combustion engine

Combustion turbine Fuel cell


ENERGY CONVERSION ENGINES

Sadi Carnot (1796-1832)

Réflexions sur la puissance motrice du feu (1824)

Christian Friedrich Schoenbein (1799–1868)

On the Correlation of Physical Forces (1846)

h

c

h TT1

QW

−=Δ

Δ=η

HST1

HG

h Δ

Δ⋅−=

Δ

Δ=η

-350

-300

-250

-200

-150

-100

-50

0

0 500 1000 1500 2000 2500 3000Temperature [K]

Ener

gy [k

J]

T·ΔS0f

ΔG0f

ΔH0f

ΔQ

ΔW

H2 + ½ O2 → H2O

0%

20%

40%

60%

80%

100%

0 200 400 600 800 1000 1200 1400 1600Th [K]

Effic

ienc

y

TC = 298 K

600 K

900 K

HST1 hFC Δ

Δ⋅−=η

h

cC T

T1−=η

Sir William R. Grove (1811–1896)


WATER FORMATION

-350

-300

-250

-200

-150

-100

-50

0

0 500 1000 1500 2000 2500 3000Temperature [K]

Ener

gy [k

J]

T·ΔS0f

ΔG0f

ΔH0f

ΔQ

ΔW

H2 + ½ O2 → H2O

H2 O2

H2O

OH-

e-

e-

Anode Cathode

ElectrolyteKOH/H2O

H OH-

H2

H2O

R

H2O

O2

O2

H2 O2

H2O

O2-

e-

e-

Anode Cathode

Electrolytesolid oxide

H O2-

H2

H2O

R

O2-

O2

O2

H2 O2

H2O

CO32-

e- e-

Anode Cathode

Electrolytemoltencarbonate

H CO32-

H2

H2O

R

CO32-

O2

CO2

CO2 CO2

CO2

CO2

CO2

O2

H2 O2H+

e-e-

Anode Cathode

PEM

H H+

H2

H2O

H2O

R

H+

O2

O2

HYDROGEN FOR MOBILITY

Austin A40 (1966)

Tupolev 155 (1988) Hindenburg (1937)

Necar 1 (1994)

Necar 4 (2002)

NuBus, 250kW (2002)

Space Shuttle (1981-)

BMW (1978-)

Saturn (1963-) Hy.move (2009)

Ref.: Ch. Bach, Empa

0

50

100

150

200

0 10 20 30

Hy

dro

ge

n d

en

sit

y [

kg

/m3

]

Hydrogen density [kg H2/ 100kg storage material] Andreas Züttel, Switzerland, 17.07.14

HYDROGEN DENSITY

carbon hydrates liq. hydro-

carbons

metal hydrides

comp. H2 gas

liq. H2

liq. natural gas

NH3

complex hydrides

physisorption

ENERGY DENSITY OF FUELS

10

20

5 10 15

Vol.

Ene

rgy

dens

ity [k

Wh/

l]

Grav. Energy density [kWh/kg]

Coal

Oil Metal hydride

Complex hydride

Butane

Alcohol

liq. H2

→

Wood comp. H2

Battery

POWER PLANT APPLICATIONS

Steam generator 100 MW

FUEL LEAK SIMULATION

Before ignition t = 0 s

Ref.: Michael R. Swain, University of Miami, Coral Cables, FL 33124, USA

Hydrogen powered vehicle on the left. Gasoline powered vehicle on the right.

Ignition of both fuels occur. Hydrogen flow rate 2100 SCFM (0.18 m3/min.)

Gasoline flow rate 680 cm3/min.

Ignition t = 3 s

Andreas Züttel, University of Fribourg, 17.07.14

FUEL LEAK SIMULATION

t = 60 s

Ref.: Michael R. Swain, University of Miami, Coral Cables, FL 33124, USA

Hydrogen flow is subsiding, view of gasoline vehicle begins to enlarge

Hydrogen flow almost finished. View of gasoline powered vehicle has been expanded to nearly full screen.

t = 90 s

New York / Lakehurst, May 6th 1937, 6 pm

Accident: While the airship was landing she has got on fire about 80 meters above ground level and crashed. Fatalities: 13 of 36 passengers, 22 of 60 crew members 1 member of 228 ground staff holding the ship.

LZ 129 “HINDENBURG”

Andreas Züttel, University of Fribourg, 15.12.2002 45

CAUSE OF FIRE

New investigation: The inflammable skin of the Hindenburg was ignited by an electric discharge arc between the electrostatic charged skin and the grounded metallic frame.

Ref.: Addison Bain, Wm. D. Van Vorst, "The Hindenburg tragedy revisited: the fatal flaw found", Int. Journal of Hydrogen Energy 24 (1999), pp. 399-403

Paris / July 25th 2000, 4:44 pm

Accident: While the jet was taking off flames were noticed at the rear side of the left side wing. All on board were killed: 9 crew, 100 passengers 4 people were killed on the ground. 5 injured on the ground, one seriously

AF 4590 CONCORDE

VCard: A. Züttel

HYDROGEN IN MATERIALS: FUNDAMENTALS AND APPLICATIONSmh2014.salford.ac.uk › cms › resources ›...

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