Neutrons for Hydrogen Storage: Dynamics - Kinetics - Reactions Science... · Important properties...
Transcript of Neutrons for Hydrogen Storage: Dynamics - Kinetics - Reactions Science... · Important properties...
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Neutrons for Hydrogen Storage: Dynamics - Kinetics - Reactions
A. Borgschulte,1 E. Callini,1 R. Gremaud,1 E. R. Andresen,3 P.Hamm,3 A. J. Ramirez-Cuesta,2 S. I. Orimo,4 A. Züttel1, F. Zamponi,5 M. Woerner,5 T. Elsaesser5
1Empa, Swiss Federal Laboratories for Materials Testing and Research, Hydrogen & Energy, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland
2ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, United Kingdom
3Physikalisch-Chemisches Institut, Universität Zürich, Zürich, Switzerland
4Institute for Materials Research (IMR), Tohoku University, Japan
5Max-Born Institut, Berlin, Germany
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2Andreas Züttel, Switzerland, 9/26/20122
Hydrogen – solid interactions
Hydrogen & metal Physisorption Chemisorption
Solid solution (-phase) Hydride (-phase) Complex hydride
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3
0 250 500 750 1000 1250 1500-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
0
5
10
15
20
25w
eigh
t cha
nge
(mas
s.%
)
time (min)
pres
sure
(bar
)
0.0 0.5 1.0 1.50.1
1
10
absorption
desorption
LaNi5Hx @ 24.5°C
equi
libriu
m p
ress
ure
(bar
)Hydrogen content x (mass%)
Gravimetric pcT measurements on LaNi5H6
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4
Thermostatic properties: hydrogen content, enthalpies and entropy of all involved phases
Empirical kinetics: meta-stable phases (impurities), time dependence of phase changes (hydrogen evolution / uptake)
Important properties in Hydrogen storage in metal hydrides
This is all the industry needs to know to built a hydrogen storage.However,
if we want to know why, or try to design new materials, knowledge of
Crystal structure of all involved phases Morphology, surface structure of all involved phases
Dynamic processes: transient bulk phases Dynamic surface processes Vibrational structure Diffusion
…might be helpful
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Empa, , 5
Bragg peak
Phonon side bands
Elastic scattering: E=0Diffraction, SANS
Inelastic scattering: E0Phonons, Magnons,...quantized modes, periodic motions selection rules:Eneutron= Ephononkneutron= kphonon
Quasielastic scattering: E~0stochastic, non-periodicmotions
Elastic, inelastic, quasielastic scattering of neutrons
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6
Neutron diffraction … see talks of John Irvine, Bill David…
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Empa, , 7
Bragg peak
Phonon side bands
Elastic scattering: E=0Diffraction, SANS
Inelastic scattering: E0Phonons, Magnons,...quantized modes, periodic motions selection rules:Eneutron= Ephononkneutron= kphonon
Quasielastic scattering: E~0stochastic, non-periodicmotions
Elastic, inelastic, quasielastic scattering of neutrons
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8
Vibrational Spectroscopy
Raman light scattering
Infrared spectroscopy
Inelastic neutron scattering
LiBD4
LiBH4
HT-LiBH4
S. Gomes, H. Hagemann, K. Yvon, JalCom 346 (2002) 206–210A. Borgschulte, et al., Faraday Discuss. 2011, 151, 213.
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Structures of Ca(BH4)2
H = 35 meV/Ca(BH4)2
H = 69 meV/Ca(BH4)2
STHG
Fddd
P42/m
Pbca
F. Buchter et al., J. Phys. Chem. C 113, 17223 (2009).
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Total density of phonon states by DFT
kTE
eEgdEkS 1ln
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Free energy as a function of temperature
F. Buchter et al., J. Phys. Chem. C 113, 17223 (2009).
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Experimental and calculated density of H phonon states
A. Borgschulte, et al., Phys. Rev. B 83, 024102 (2011).
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13
BH4-Vacancy
Enjoy the beauty of the theory of diffusion
Li vacancy
= Schottky defect
Ref.: Z. Lodziana, to be published
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Empa, , 14
Bragg peak
Phonon side bands
Elastic scattering: E=0Diffraction, SANS
Inelastic scattering: E0Phonons, Magnons,...quantized modes, periodic motions selection rules:Eneutron= Ephononkneutron= kphonon
Quasielastic scattering: E~0stochastic, non-periodicmotions
Elastic, inelastic, quasielastic scattering of neutrons
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j
tiQsiQstiinc
k j
tiQsiQsticoh
jjkj eeedteeedt
ddd
)()0()()0(
2
Theory: Scattering of neutrons
j k k+1…j+1…
tisi
FTN
j
tsiQsiQ etQIdtQSeeN
tQI jj
),(
21),(1,
1
)()0(
intermediate scattering function dynamic structure factor
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QENS derivative of jump diffusion (I)
N
jj trPtsrP
Nt
trP 1,,1
,
iQretrPdrtQI ,,
G.T.Chudley and R.J. Elliott, Proc. Phys. Soc. 77, 353 (1961)
Lorentzian curve, width /)(Qf
j
j
iQs
N
j
Qs
eN
ttQI
tQIeNt
tQI
1/exp,
,11,1
I(Q,t)
t
22 /)(/)(),(),(
QfQfetQIdtQS ti
FT
S(Q,)
FT
)(Qf
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simple case of hydrogen hopping on interstitial sites forming a simple-cubic structure.
2261
0)(lim,1)( sQQfe
NQf
Q
iQs j
22 )6/()( DQQQf
)6/(2 sD
Q is small:
Einstein-Smoucholski equation:
QENS derivative of jump diffusion (II)
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QENS-measurements on liquid LiBH4
P. Martelli et al., J. Phys. Chem. A 2010, 114, 10117
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/scmK)D(TDQ
25
2
106600
Q-dependence of the width
P. Martelli et al., J. Phys. Chem. A 2010, 114, 10117
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-15 -10 -5 0 5 10 15 900 950 1600 1700 1800
Inte
nsity
(arb
. uni
ts)
chemical shift (ppm)
300 K
400 K
3'31
Inte
nsity
(nor
m. u
nits
)
Raman shift (cm-1)
f
300 K
402 K
2
QUENS
NMR Raman
Mobility in LiBH4 by spectroscopy (Rotational diffusion)
principle of “line-shape analysis”signal in frequency space
=Fourier transform of thetime correlation function
(= changes in time)
HT-LiBH4
LT-LiBH4
LT-LiBH4
HT-LiBH4
A. Remhof, et al. Phys. Rev. B 2010, 81, 214304; A. Borgschulte, et al., Faraday Discuss. 2011, 151, 213
energy uncertainty
E
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Time and space resolution of spectroscopy
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1000 750 500 300 2501E-15
1E-14
1E-13
1E-12
1E-11
1E-10
1E-9
1E-8
1E-7
1E-6
1E-5
1E-4
1E-3250 300 350 400 450 500 550 600 650 700
H in MgH2H in NaH
BH4 in LiBH4
Li in graphite
Li in V2O5
H in LaNi5
H in V
H in Ta
H in Pd
H in Ni
diffu
sion
par
amet
er D
(cm
2 /s)
temperature T (K)
1000/T (10-3 K-1)Comparison:Hydrogen Diffusion
Dtx 4
water in pasta:1 mm in 5 min
H in NiMH batteries~ 10 m in min
Li in Li-ion batteries~ m in min
H in ionic/covalent hydridesm in days
Li in LiBH4
H exchange: 10 orders lower
1 2 3 4
0.1ps
0.1 s
H in complex hydridesm in days
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23
BH4-Vacancy
There is more than diffusion taking place
Li vacancy
= Schottky defect
Ref.: Z. Lodziana, to be published
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slowdetector
probebeam
pumpbeam
sample
delay
Measurement of the time correlation function directly:Pump – probe experiments
S(Q,)
FT
I(Q,t)
t
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IR-pump excites a vibration; IR-probe measures the ensuing changes
|10>
|00>
|20>
(ps time resolution, IR-probe: 100 fs)
Pum
p fre
quen
cy [a
.u.]
Probe frequency [a.u.]
2D-IR pump-probe spectrometer (“femto-chemistry”)
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Decay of stretching modes 1.5 ps
Rise of temperature 3 ps (libration + external)
1.5 <> 3.0, so there must be intermediate step (bending)
0 10 20 30
0.00
0.02
0.04
0.06
probe = 2186 cm-1
Exp. fit, = 3.0 ps
A
[mO
D]
Delay [ps]
0 10 20 300.0
0.5
1.0
1.5
2.0 probe = 1668 cm-1
Fit, = 1.6 ps
A
[mO
D]
Delay [ps]
IR-pump, t=0
E.R. Andresen, R. Gremaud, A. Borgschulte, A.J. Ramirez-Cuesta, A. Züttel, and P. Hamm, J. Phys. Chem. A 113, 12838 (2009)
Vibrational relaxation pathway
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Polarization experiments probing reorientation
highintensity
lowintensity
pump probe
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Polarization-dependent measurements:Reorientational motions
1660 1680 1700 1720 1740 1760 1780-100-80-60-40-20
020406080
100 0
20
40
60
80
100
0.1 1 100.0
0.2
0.4
010203040506070
ESA
A [
OD
]
Probe frequency [cm-1]
1 ps 4 ps 2 ps 8 ps
A [
OD
]
Magic-angle
probe = 1667.6 cm-1
= 1.6 ps
Anis
otro
pyDelay [ps]
Averaged anisotropy
probe = 1653.5 - 1672.3 cm-1
Abso
rban
ce [m
OD
]
2para perp
para perp
I IA
I I
Neither BH4 rotation, northermal motion observedwithin 5 ps
Anisotropy
R. Gremaud,et al., Materials Research Society Symposium Proceedings 1216, pp. 111-116 (2010).
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Comparison with QENS
5 ps
R. Gremaud,et al., Materials Research Society Symposium Proceedings 1216, pp. 111-116 (2010).A. Remhof et al. Phys. Rev. B 81, 214304 (2010)
LiBH4-LT
LiBH4-HT
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Femtosecond X-ray diffraction
Woerner et al. J. Chem. Phys. 133, 064509 (2010)
Zamponi et al. Opt. Express 18, 947 (2010)
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z = 2.14 => Li0.86+
z = 9.86 => BD40.86-
A fs photon pulse runs through a LiBH4 crystal
with/without
electric field
BH4-Li+
Electric field from Laser, E = 1.5 eV << Egap Laser intensity ~4x1011 W/cm2
F. Buchter et al. Phys. Rev. B 83, 064107 (2011).
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Femtosecond X-ray diffraction on LiBH4
J. Stingl, F. Zamponi, B. Freyer, M. Woerner, T. Elsaesser, and A. Borgschulte, accepted by PRL (2012)
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Is this possible with neutrons?
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Time-resolved quasielastic neutron scattering studies of native photosystems
J. Pieper et al. Phys. Rev. Lett. 100, 228103 (2008)
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NMR
Neutrons?IR/UV-vis
Raman
XRD
EPR
in
out
XAS
Mössbauerproduct detectionIRMSGC…
Operando approach
Time-resolution by modulated excitation spectroscopy
see, e.g., D. Ferri et al, Phys. Chem. Chem. Phys. 2010, 12, 5634;C. F. J. König et al., JPC ASAP (2012).
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Neutron scattering gives an insight into hydrogen storage in hydrides
Neutron diffraction and inelastic neutron scattering are perfect tools for equilibrium properties
Simple (rotational diffusion, jump diffusion) and fast (ps~ns) time dependent processes can be investigated by quasi-elastic neutron scattering
modulation excitation spectroscopy might bridge the gap
optical spectroscopy is the perfect complementary method
Summary and Outlook
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37
1. After 1850: Rate constants:(Ludwig Wilhelmy, Poggendorfs Ann. 81 (1850) 413, 499)Quantitative time dependence
2. After ~1900: Reaction mechanisms and Elementary ReactionsIncreasing detail, complexity, sophistication(van’t Hoff, Arrhenius, Amsterdam 1903)
3. After 1950: 1st time resolved experimentsRelaxation techniques, Flash Photolysis, Shock waves, chemical exchange by NMR, molecular beams
4. After ~1960: Laser Pump-Probe Techniques=> ns (1960) => ps (1970) => x fs (1980) => fs (1990) => as (2000)
M. Quack, Chimia 57 (2003) 147–160
Reaction dynamics on simple systems
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383
EQUILIBRIUM Phase diagram Hydrogen in Metals
H(
½ (H2)=
H(
½ (H2)=
-Phase: Solid Solution -Phase: Hydride Phase
MinxxxGi
ii
is temperature dependent => Van ‘t Hoff R
SRTH
pp H
0
021 2ln
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
0.01
0.1
1
10
100
p(b
ar)
x (H/M)
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0 2 4 6 80.1
1
10
100
LiBH4 @ T = 491°C NaAlH4 @ T = 130°C LiNH2 @ T = 260°C
3 NaH + Al + 3/2 H2 <= Na3AlH6
<= LiNH2 + LiHLi2NH + H2
Na3AlH6 + 2 Al + 3/2 H2 <= 3NaAlH4
LiH + B + 3/2 H2 <= LiBH4
hydr
ogen
pre
ssur
e (b
ar)
m/m (%)
Phase diagram Hydrogen in Complex Hydrides
Ref.: Ce-doped NaAlH4 (Lohstroh2007), LiBH4 (Mauron2007), and LiNH2+LiH (David2007)
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3 NaAlH4
=> Na3AlH6 + 2Al + 3 H2
=> 3 NaH + 3Al + 9/2 H2
= 5.6 mass %
50 100 150 200 250 300-6
-5
-4
-3
-2
-1
0
mas
s lo
ss (%
)
temperature (°C)50 100 150 200 250 300
-6
-5
-4
-3
-2
-1
0
mas
s lo
ss (%
)
temperature (°C)
Thermo - Desorption of pure and Ti-doped NaAlH4
Constant p = 1.5bar H2,Heating rate 1 K/min
B. Bogdanovic, M. Schwickardi, J. Alloys Compd. 253–254 (1997) 1.
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Small-angle neutron scattering
S. Sartori et al. Nanotechnology 20 (2009) 505702
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Hydrogen supply
Ar-glove box
Balance electronics
sam
ple
balance
Measurement principle to correct for buoyancy contribution to the sample mass.
Gravimetric hydrogen sorption measurements
“Sieverts” Pressure automation
bala
nce
(100
...20
0 m
l)
pressure 0...200 bars
vacuum
hydrogen
E E
p
valve , 1 2
time