this talk an example of high-throughput materials research · rg 112 uub 113 uut 114 uuq 115 uup...
TRANSCRIPT
1
An example of high-throughput materials research
Ronald Griessen, Nov.1, 2007
This talk
The problem: energy storageHow to find new hydrogen storage materialsThe idea behind hydrogenographyThe Mg-Ti-Ni-H system
Measuring isotherms, enthalpies and entropies opticallyFinding a destabilized Mg-based hydride
Hydrogenography works also for metallic hydridesBulk, nanocrystals and thin filmsCatalystsConclusions
This talk
The problem: energy storageHow to find new hydrogen storage materialsThe idea behind hydrogenographyThe Mg-Ti-Ni-H system
Measuring isotherms, enthalpies and entropies optically
Finding a destabilized Mg-based hydrideHydrogenography works also for metallic hydridesBulk, ball milling and thin filmsCatalystsConclusions
The electrical cycle
Sun
ENERGY
ENERGY
The hydrogen cycle
O2
O2
H2
H2
H2O
Dissociation of water
TransportStorage
CombustionFuel cells
H2 O2
Sun
ENERGY
ENERGY
Li-ion battery0.84 MJ/kg
Battery Toyota Prius0.12 MJ/kg
Electrons Hydrogen now
2
Electrons Hydrogen now
Li-ion battery0.84 MJ/kg
Battery Toyota Prius0.12 MJ/kg
H in modified Prius “LaNi5H6”
1.9 MJ/kg
Electrons Hydrogen tomorrow
Li-ion battery0.84 MJ/kg
Battery Toyota Prius0.12 MJ/kg
NaAlH4 9 MJ/kgTi(AlH4)4 11 MJ/kgLiAlH4 12 MJ/kg LiBH4 22 MJ/kgAl(BH4)3 24 MJ/kg
Mg2NiH4 4.5 MJ/kg
9
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0.01
0.1
1
10
100
1000
591 K
493 K
413 K
363 K
293 K
Hyd
roge
n pr
essu
re (1
05 Pa)
Hydrogen concentration H/Pd
Pressure-composition isotherms of PdHx
1.0 1.5 2.0 2.5 3.0 3.5 4.01E-3
0.01
0.1
1
10
100
1000
Hyd
roge
n pr
essu
re (1
05 Pa)
1000/T
0
ln H SpRT RΔ Δ
= −
10
1.0 1.5 2.0 2.5 3.0 3.5 4.010-3
10-2
10-1
100
101
102
Pre
ssur
e[1
05P
a]
1000/T [K]
This talk
The problem: energy storageHow to find new hydrogen storage materials
The idea behind hydrogenographyThe Mg-Ti-Ni-H system
Measuring isotherms, enthalpies and entropies optically
Finding a destabilized Mg-based hydrideHydrogenography works also for metallic hydridesBulk, ball milling and thin filmsCatalystsConclusions
Group 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18Period
1 1 H 2
He
2 3 Li
4 Be 5
B 6 C
7 N
8 O
9 F
10Ne
3 11Na
12 Mg 13
Al 14 Si
15 P
16S
17Cl
18Ar
4 19K
20 Ca
21Sc
22Ti
23V
24Cr
25Mn
26 Fe
27 Co
28 Ni
29 Cu
30 Zn
31 Ga
32 Ge
33 As
34Se
35Br
36Kr
5 37Rb
38 Sr
39Y
40Zr
41Nb
42Mo
43Tc
44 Ru
45 Rh
46 Pd
47 Ag
48 Cd
49 In
50 Sn
51 Sb
52Te
53I
54Xe
6 55Cs
56 Ba * 71
Lu72Hf
73Ta
74W
75Re
76 Os
77 Ir
78 Pt
79 Au
80 Hg
81 Tl
82 Pb
83 Bi
84Po
85At
86Rn
7 87Fr
88 Ra ** 103
Lr104Rf
105Db
106Sg
107Bh
108 Hs
109 Mt
110 Ds
111 Rg
112 Uub
113 Uut
114 Uuq
115Uup
116Uuh
117Uus
118Uuo
*Lanthanoids * 57La
58Ce
59Pr
60Nd
61Pm
62 Sm
63 Eu
64 Gd
65 Tb
66 Dy
67 Ho
68 Er
69 Tm
70Yb
**Actinoids ** 89Ac
90Th
91Pa
92U
93Np
94 Pu
95 Am
96 Cm
97 Bk
98 Cf
99 Es
100 Fm
101Md
102No
Periodic System
3
Group 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18Period
1 1 H 2
He
2 3 Li
4 Be 5
B 6 C
7 N
8 O
9 F
10Ne
3 11 Na
12 Mg 13
Al 14 Si
15 P
16S
17Cl
18Ar
4 19 K
20 Ca 21
Sc 22 Ti
23 V
24 Cr
25 Mn
26 Fe
27Co
28 Ni
29 Cu
30 Zn
31 Ga
32 Ge
33 As
34Se
35Br
36Kr
5 37 Rb
38 Sr 39
Y 40 Zr
41 Nb
42 Mo
43 Tc
44 Ru
45Rh
46 Pd
47 Ag
48 Cd
49 In
50 Sn
51 Sb
52Te
53I
54Xe
6 55 Cs
56 Ba * 71
Lu 72 Hf
73 Ta
74 W
75 Re
76 Os
77Ir
78 Pt
79 Au
80 Hg
81 Tl
82 Pb
83 Bi
84Po
85At
86Rn
7 87 Fr
88 Ra ** 103
Lr 104 Rf
105 Db
106 Sg
107 Bh
108 Hs
109Mt
110 Ds
111 Rg
112 Uub
113 Uut
114 Uuq
115 Uup
116Uuh
117Uus
118Uuo
*Lanthanoids * 57 La
58 Ce
59 Pr
60 Nd
61 Pm
62 Sm
63Eu
64 Gd
65 Tb
66 Dy
67 Ho
68 Er
69 Tm
70Yb
**Actinoids ** 89 Ac
90 Th
91 Pa
92 U
93 Np
94 Pu
95Am
96 Cm
97 Bk
98 Cf
99 Es
100 Fm
101 Md
102No
Light ternary compounds
AB 6 x 19 = 114
ABC 6 x 10 x 9 = 540
ABCD 6 x 10 x 9 x 9 = 4869
ABC 6 x 10 x 9 = 540
Discharge capacity of MgyTi1-y films
Vermeulen, Niessen and Notten, Electrochem. Comm. (2005)
y in MgyTi1-y
High rate
Low rate
NiMH 300 mAh/g ~1 MJ/kg
Group 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18Period
1 1 H 2
He
2 3 Li
4 Be 5
B 6 C
7 N
8 O
9 F
10Ne
3 11 Na
12 Mg 13
Al 14 Si
15 P
16S
17Cl
18Ar
4 19 K
20 Ca 21
Sc 22 Ti
23 V
24 Cr
25 Mn
26 Fe
27Co
28 Ni
29 Cu
30 Zn
31 Ga
32 Ge
33 As
34Se
35Br
36Kr
5 37 Rb
38 Sr 39
Y 40 Zr
41 Nb
42 Mo
43 Tc
44 Ru
45Rh
46 Pd
47 Ag
48 Cd
49 In
50 Sn
51 Sb
52Te
53I
54Xe
6 55 Cs
56 Ba * 71
Lu 72 Hf
73 Ta
74 W
75 Re
76 Os
77Ir
78 Pt
79 Au
80 Hg
81 Tl
82 Pb
83 Bi
84Po
85At
86Rn
7 87 Fr
88 Ra ** 103
Lr 104 Rf
105 Db
106 Sg
107 Bh
108 Hs
109Mt
110 Ds
111 Rg
112 Uub
113 Uut
114 Uuq
115 Uup
116Uuh
117Uus
118Uuo
*Lanthanoids * 57 La
58 Ce
59 Pr
60 Nd
61 Pm
62 Sm
63Eu
64 Gd
65 Tb
66 Dy
67 Ho
68 Er
69 Tm
70Yb
**Actinoids ** 89 Ac
90 Th
91 Pa
92 U
93 Np
94 Pu
95Am
96 Cm
97 Bk
98 Cf
99 Es
100 Fm
101 Md
102No
Light Mg-Ti-Ni ternary alloys
Mg100-x-y Tix Niy=4950
Looking efficiently for a needle in a huge haystack
This talk
The problem: energy storageHow to find new hydrogen storage materialsThe idea behind hydrogenography
The Mg-Ti-Ni-H system Measuring isotherms, enthalpies and entropies
opticallyFinding a destabilized Mg-based hydride
Hydrogenography works also for metallic hydridesBulk, ball milling and thin filmsCatalystsConclusions
Switchable mirrorsYttrium
Y: Metal
YH2 : Metal
YH3 : Insulator
4
Switchable mirrors: “seeing” hydrogen
in air
in H2
Yttrium Mg-TiThis talk
The problem: energy storageHow to find new hydrogen storage materialsThe idea behind hydrogenographyThe Mg-Ti-Ni-H system
Measuring isotherms, enthalpies and entropies opticallyFinding a destabilized Mg-based hydride
Hydrogenography works also for metallic hydridesBulk, ball milling and thin filmsCatalystsConclusions
Bernard Dam
Sputtering system for new H storage materials22
Mg
Ti
PdNi
23
Mg
Ti
PdNi
Mg
Ti
Ni
24
Mg
Ti
PdNi
Mg
Ti
Ni
5
Robin Gremaud26
Mg
Ti
Ni
Optical transmission of Mg-Ti-Ni during hydrogenationT=333 K
Pressure
0 Pa
105 Pa
27
Optical transmission in ternary diagram
Mg at. fraction y0.4 0.5 0.7 0.8 0.9 1 MgTi 0.6
Ni
0.1
0.2
0.3
0.4
0.5
0.6
Ni
Ti Mg
Mg0.69Ni0.26Ti0.05
R. Gremaud et al. Advanced Materials 19 (2007) 2813-2817
28
Isotherms for each pixel
Mg at. fraction y0.4 0.5 0.7 0.8 0.9 1 MgTi 0.6
Ni
0.1
0.2
0.3
0.4
0.5
0.6
100
101
102
0.0 0.2 0.4 0.6 0.8
Mg0.69Ni0.26Ti0.05
log(T/T0)
p H2 (m
bar)
313 K
323 K333 K
353 K363 K
~Hydrogen concentrationR. Gremaud et al. Advanced
Materials 19 (2007) 2813-2817
29
Van ‘t Hoff plot for each pixel
2.7 2.8 2.9 3.0 3.1 3.2
101
102370 360 350 340 330 320 310
p eq (m
bar)
1000/Temperature (K-1)
ΔH = -40 kJ/molH2
Mg0.69Ni0.26Ti0.05
Temperature (K)
Mg at. fraction y0.4 0.5 0.7 0.8 0.9 1 MgTi 0.6
Ni
0.1
0.2
0.3
0.4
0.5
0.6
0
ln H SpRT RΔ Δ
= −
R. Gremaud et al. Advanced Materials 19 (2007) 2813-2817
30
Map of hydride formation enthalpies
Mg at. fraction y0.4 0.5 0.7 0.8 0.9 1 MgTi 0.6
Ni
0.1
0.2
0.3
0.4
0.5
0.6
R. Gremaud et al. Advanced Materials 19 (2007) 2813-2817
6
31
Van ‘t Hoff plots for Mg-based hydrides
1.5 2.0 2.5 3.0 3.510-5
10-4
10-3
10-2
10-1
100
101600 500 400 300
10-5
10-4
10-3
10-2
10-1
100
101(1)
Mg0.69 Ni
0.26 Ti0.05 H
1.1
nano MgH2 (2)
nano Mg2 NiH
4(2)
Mg0.85 Ti
0.15 H1.6
Mg2 NiH
4
p eq [b
ar]
1000/T [K-1]
TF MgH2
(4)
bulk PdH0.6
(1) G. Liang et al., J. Alloys Compd. 282 286 (1999)(2) G. Liang et al., J. Alloys Compd. 267 302 (1998)
(4) A. Krozer and B. Kasemo, J. Less-Common Met. 160 323 (1990)
Temperature [K]
Mg0.69Ni0.26Ti0.05
3.2 wt%
This talk
The problem: energy storageHow to find new hydrogen storage materialsThe idea behind hydrogenographyThe Mg-Ti-Ni-H system
Measuring isotherms, enthalpies and entropies opticallyFinding a destabilized Mg-based hydride
Hydrogenography works also for metallic hydrides
Bulk, ball milling and thin filmsCatalystsConclusions
33
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.81
10
100
Pd on Plastic 6 cycle
Pd on Quartz 6 cycle
Pres
sure
[mba
r]
ln(T/To)
296 K
Pressure-optical transmission-isotherm
α
34
Optical determined Van ‘t Hoff plots for PdHx
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.410-3
10-2
10-1
100
101550 500 450 400 350 300
Desorption AbsorptionP
ress
ure
[Bar
]
1/Temperature [1000/K]
Temperature T [K]
0
ln H SpRT RΔ Δ
= −
-92.5±1.3-39.0±0.5
-97.5±0.8-41.0±0.4
-96.0±1-41.1±0.4
ΔS0β→α
[J/K/molH2]ΔHβ→α[kJ/molH2]
-92.5±1.3-39.0±0.5
-97.5±0.8-41.0±0.4
-96.0±1-41.1±0.4
ΔS0β→α
[J/K/molH2]ΔHβ→α[kJ/molH2]
E. Wicke and H. Brodowsky, Hydrogen in Metals II, G. Alefeld an J. Völkl ed. (1978)
R. Lässer, K.-H. Klatt, PRB 28, 748
This talk
The problem: energy storageHow to find new hydrogen storage materialsThe idea behind hydrogenographyThe Mg-Ti-Ni-H system
Measuring isotherms, enthalpies and entropies opticallyFinding a destabilized Mg-based hydride
Hydrogenography works also for metallic hydridesBulk, nanocrystals and thin films
CatalystsConclusions
36
FCC+BCC
FCC BCC
Cu Fe
Phase boundaries of Cu-Fe prepared differently
the equilibrium phase boundary at room temperature
liquid quenching
thermal evaporation
sputtering
sputtering on cryogenic substrates
mechanical alloying (nanocrystalline)
Cu FeE. Ma, Progress in Materials Science 50 (2005) 413–509
7
37
Comparison: films - nanocrystals
0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 00
1
2
3
4
5
6
7
8
Enth
alpy
of f
orm
atio
n (k
J/m
ol)
C o n c e n tra t io n o f A g (a t% )0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0
0
1
2
3
4
5
6
7
8
Enth
alpy
of f
orm
atio
n (k
J/m
ol)
C o n c e n tra t io n o f A g (a t% )
sputter-deposited fcc solution terminal fcc solutions from literature ball milled fcc solution
This talk
The problem: energy storageHow to find new hydrogen storage materialsThe idea behind hydrogenographyThe Mg-Ti-Ni-H system
Measuring isotherms, enthalpies and entropies opticallyFinding a destabilized Mg-based hydride
Hydrogenography works also for metallic hydridesBulk, nanocrystals and thin filmsCatalysts
Yttrium or any switchable mirror material
Catalyst, e.g. Pd
Light source
Optical screening for hydrogen storage properties
3 CCDCamera
substrate200 nm yttrium filmmetallic Y insulating YH3
substrate200 nm yttrium film
A. Borgschulte et al J. Catalysis 239 (2006) 263-271
Critical Pd thickness
substrate200 nm yttrium filmmetallic Y insulating YH3
0 100 200 300 4000.0
0.5
1.0
1.5
2.0
3 nm
4 nm
5 nm
6 nm
7 nm
8 nm
trans
mis
sion
(arb
. u.)
time (s)
At least 4 nm Pd are needed for H absorption
A. Borgschulte et al J. Catalysis 239 (2006) 263-271
is “universal”is “quantitative” for hydride formation and kinetics.can be used for:
batteriescatalytic caplayersadaptive solar collectors optical fiber H sensors.
Thin films are not exotic ! Theory feedback is essential
8
Jan Rector
Herman Schreuders
Chase Broedersz
AndreasBorgschulte
PhilippeMauron
DanaBorsa
BernardDam
MartaGonzalez
AndreaBaldi
Robin Gremaud
WLo
T ank you H2