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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
Andreas Züttel, Switzerland, 17.07.14 3
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
Andreas Züttel, Switzerland, 17.07.14 5
HYDROGEN ISOTOPES
H D T
Andreas Züttel, Switzerland, 17.07.14 6
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
Andreas Züttel, Switzerland, 17.07.14 7
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
−+−+
−+=
Andreas Züttel, Switzerland, 17.07.14 9
PRIMITIVE PHASEDIAGRAM OF HYDROGEN
Ref: W. B. Leung, N. H. March and H. Motz, Physics Letters 56A (6) (1976), pp. 425-426
RT
Andreas Züttel, Switzerland, 17.07.14 10
MOLECULAR HYDROGEN
2
2
Vna
bnVTRn)V(p ⋅−⋅−
⋅⋅=
Andreas Züttel, Switzerland, 17.07.14 11
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)
Andreas Züttel, Switzerland, 17.07.14 13
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
Andreas Züttel, Switzerland, 17.07.14 15
HYDROGEN STORAGE DENSITY
Dynatek
HYDROGEN STORAGE VESSELS
Ref: Dynetek Europe GmbH, Breitscheider Weg 117a, D-40885 Ratingen, URL: http://www.dynetek.de
Andreas Züttel, Switzerland, 17.07.14 17
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
Andreas Züttel, Switzerland, 17.07.14 18
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
Andreas Züttel, Switzerland, 17.07.14 21
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
Andreas Züttel, Switzerland, 17.07.14 26
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)
Andreas Züttel, Switzerland, 17.07.14 34
ENERGY CONVERSION DEVICES
Steam engine
Steam turbine
Internal combustion engine
Combustion turbine Fuel cell
Andreas Züttel, Switzerland, 17.07.14 35
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)
Andreas Züttel, Switzerland, 17.07.14 36
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
physi- sorption
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