Complex Metal Hydrides For Reversible Hydrogen Storage: Vitalie Stavila

Complex metal hydrides for
reversible hydrogen storage
Vitalie Stavila
Sandia National Laboratories
*E-mail: vnstavi@sandia.gov
Sandia is a multi program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the
U.S. Department of Energys National Nuclear Security Administration under contract DE-AC04-94AL85000
Energy Storage Workshop, Santa Clara, CA, April 29, 2010
Hydrogen as a fuel
Biomass
Hydro
Wind
Solar
Hydrogen gas has almost three

times energy content of gasoline
(120 MJ/kg vs. 44 MJ/kg)
H2 Fuel Cells reach >80% efficiency
in combined heat and power
generation and >50% in electrical
Nuclear
Oil
Coal
Natural
Gas
No natural source of hydrogen;

difficult/expensive to produce
Low density of H2 gas and liquid
=> low volumetric energy content
Volumetric compression and
storage is problematic
Solid-state hydrogen storage, Ed. G. Walker, 2008.
2/20
Hydrogen for transportation

Metal hydrides represent a class of materials with volumetric densities
higher than gaseous or liquid hydrogen.
Volume Comparisons for 4 kg Vehicular H2 Storage
110L
26L
33L
57L
Mg2FeH6
LaNi5H6
H2 (liquid)
H2 (200 bar)
Schlapbach & Zttel, Nature, 2001, 296.
3/20
Complex metal hydrides

N. Stetson & G. Sandrock (DOE)
Material Capacity vs. Temperature
4/20
Borohydrides for hydrogen storage

Metal borohydrides represent a class of materials with high gravimetric and
volumetric hydrogen densities.
Density
(g/cm3)
Hydrogen
density
(kg/m3)
Hydrogen
density
(mass%)
Heat of
formation,
H, (kJ/mol)
Melting /
Decomposition*
T, oC
LiBH4
0.66
122.1
18.5
-194
278
NaBH4
1.07
114.5
10.7
-191
505
Mg(BH4)2
0.78
147.4
14.9
-226
295*
Ca(BH4)2
1.07
124.1
11.6
-302
310*
Al(BH4)3
0.79 (liq.)
133.5
16.9
-131
-64
Zr(BH4)4
1.18
126.2
10.7
-398
29*
Y. Nakamori, S. Orimo, Borohydrides as hydrogen storage materials, in Solid-state hydrogen

storage, Ed. G. Walker, 2008.
S. Orimo, Y. Nakamori, J.R. Eliseo, A. Zttel, C.M. Jensen, Chem. Rev., 2007, 107, 4111.
5/20
Reversible borohydrides
Des.
M + xB + 2xH2
M(BH4)x
Abs.
Selected examples:
Zttel et al. Scr. Mater., 2007, 56, 823
Orimo et al. J. Alloys. Comp. 2005, 404-406, 427
Soloveichik et al. Int. J. Hydrogen Energy, 2009, 34, 916
Severa et al. Chem. Commun. 2010, 46, 421
Kim et al. Scr. Mater., 2008, 58, 481
Rnnebro, Majzoub. J. Phys. Chem. C. 2007, 111, 12045
high dehydrogenation
temperatures
Problems &
Challenges
high pressure required

for rehydrogenation
contamination of H2 gas
with boron hydrides
loss of capacity upon
cycling
stable intermediates
([B12H12]2-, etc.
6/20
Hydrogen release from Ca(BH4)2

with Ewa Rnnebro and Mutlu Kartin (Sandia)
Additive Effect on Ca(BH4)2
Desorption
Life-cycle of Ca(BH4)2 with

4wt% PdCl2 Additive
7
340
wt% H2 released
Temperature, C
340
7
300
300
1st cycle
6
260
260
Temperat
ure
1st
220
220
2nd
3rd
180
Temperature
no additive
SWNT
graphite
TiCl3
NbF5
140
100
60
180
20
40
60
80
100
3rd
4th
5th
140
4th
100
5th
1
0
120
2
1
60
20
2nd
Sieverts Data
20
0
0
20
40
Time (min)
60
80
100
120
Time (min)
Results:
Additives have a significant effect on H2 release from Ca(BH4)2
Significant capacity loss observed upon cycling
7/20
140
160
180
200
Hydrogen release from Mg(BH4)2

Desorption of Mg(BH4)2 ball-milled with 5mol % TiF3 and 5mol% ScCl3
R. Newhouse, V. Stavila, S. Hwang, L. Klebanoff, J.Z. Zhang J. Phys. Chem. C 2010, 114, 5224.
Significant improvement in hydrogen desorption of Mg(BH4)2 was observed in the

presence of the TiF3/ScCl3 additive
8/20

Desorption of Mg(BH4)2 ball-milled with 5mol % TiF3 and 5mol% ScCl3
11
B MAS NMR
r=
15 kHz
desorption at 600 C
with additives
no additives
150
100
50
-50
ppm
Up to 14 wt% H2 released upon heating to 600 C

At 90 MPa and 390 C rehydrogenation of 49% for the sample with additives and 66%
for the un-doped sample with additives was observed
Energy Storage Workshop, Santa Clara, April 29, 2010
9/20
-100
MgB2 almost exclusively formed upon heating up to 600 C

Additives distributed relatively uniformly throughout the boride sample
10/20
Modeling Complex Equilibria

In collaboration with M.D. Allendorf (Sandia) and Prof. Sholls group (Georgia Tech)
DFT (enthalpy, entropy, heat capacity) and FactSage (thermochemical calculations)
(a)
(a)
10
10
H2 (g)
MgH2 (s)
LiH (l)
H2 (g)
LiBH4 (s)
MgB2 (s)
10
10
Li2B12H12 (s)
LiH (s)
-1
B (s)
-1
10
10
BH3 (g)
10
-3
Li (g)
LiH (g)
Li2 (g)
-4
LiBH4 (s)
10
10
10
-6
300
400
500
600
0.1
700
-2
10
MgB12H12 (s)
-3
10
LiH (g)
-4
Li (g)
LiH (s)
LiH (l)
B (s)
Li2B12H12 (s)
-5
10
Moles
Moles
H2 (g)
-2
10
BH3 (g)
Li2 (g)
800
900
1000
H2 (g)
MgH2 (s)
-5
10
MgB12H12 (s)
MgB2 (s)
-6
10
300
400
0.1
T/(P ) (K/(atm ))
500
600
0.08
T/(P
800
0.08
) (K/(atm
K.C. Kim, M.D. Allendorf, V. Stavila, D.S. Sholl, Phys. Chem. Chem. Phys. 2010, (in press)
700
11/20
))
900
1000
[B12H12]2- species: theory and experiment

Evidence of diborane and closo-polyborate cluster formation during borohydride
desorption reactions prompted further analysis of [B12H12]2- salts
The Prototype Electrostatic Ground State (PEGS)
technique was used for structure determination and H
estimates
Predicted
Structure
C2/c
Ca[B12H12]
Calculations were performed by Prof. E. Majzoub

(University of Missouri, St. Louis)
Several hydrogen storage reactions predicted to display favorable thermodynamics were

explored, based on the first-principle calculations reported by Ozolins et al.
Ozolins, Majzoub, Wolverton. J. Am. Chem. Soc. 2009, 131, 230-237.
Borohydride reactions:
Predicted Reactions
5Mg(BH4)2 + 2LiBH4
5Mg(BH4)2 + Ca(BH4)2
5Ca(BH4)2 + 2LiBH4
Li2B12H12 + 5MgH2 + 13H2

CaB12H12 + 5MgH2 + 13H2
Li2B12H12 + 5CaH2+ 13H2
Tc ( C)
Experimental Data:
wt% H2 (350 oC)
24.4
-29
6.0
7.7
25.7
-18
4.4
6.7
37.9
83
5.2
H300K
Theoretical
wt% H2
kJ/mol H2
8.4
12/20
[B12H12]2- Destabilization
no CaB6 up to 700 oC
CaB12H12
CaB12H12 + CaH2
CaB6 + H2
CaB12H12 + CaH2
-H2
CaB6
I, a.u.
CaB6
The presence of CaH2 decreases the

temperature required to form CaB6 by
200 oC; the magnitude of the
destabilizing effect is similar to the one
observed in metal borohydrides.
13/20
Are [B12H12]2- species reversible ?

The predicted enthalpies of the LiBH4, Mg(BH4)2 and Ca(BH4)2 dehydrogenation reactions to form
MgB12H12 and CaB12H12 suggest that the reverse processes are feasible.
Ozolins, Majzoub, Wolverton, J. Am. Chem. Soc., 2009, 131, 230.
Hot-sintering under high H2-pressure

MB12H12 + Metal hydride + H2
High-energy ball milling for 60 to 180 min
Hydrogen pressure 100 MPa in a high-temperature reactor
Temperature 550 C
Reaction time: several hours to several days
100 MPa H2
550 C
Under these conditions individual metal borohydrides display at least partial reversibility!
14/20
Rehydrogenation of [B12H12]2- salts
Results:
CaB12H12 + 5CaH2 no borohydride formation up to 500 C and 90 MPa H2
Li2B12H12 and Na2B12H12 partial hydrogenation to LiBH4 and NaBH4 at 500 C and 90 MPa H2
CaB12H12 is not susceptible to rehydrogenation reactions;
Rehydrogenation of Li2B12H12 and Na2B12H12 occurs in almost quantitative yield at high
temperatures and hydrogen pressures.
15/20
Neutron Vibrational Spectroscopy

Work done in collaboration with Dr. T. Udovic (NIST)
NVS data suggest significant conversion of Li2B12H12 and Na2B12H12 into LiBH4 and NaBH4
16/20
Borohydride-ammonia materials
Motivation: The presence of both hydridic and protic hydrogen atoms
XRD
Ca(BH4)2-NH3
MgCa(BH4)4-NH3
LiCa(BH4)3-NH3
2
The BH4-NH3 compounds display increased air- and

moisture stability compared to the initial borohydrides
Ca(BH4)2NH3, MgCa(BH4)4NH3 and LiCa(BH4)3NH3
adducts release significant amounts of NH3 upon
heating, confirmed by gas phase analysis
New systems based on transition metals (e.g. Ti(III)
and Mn(II)) are currently under investigation
% weight loss
TGA
Ca(BH4)2-NH3
MgCa(BH4)4-NH3
LiCa(BH4)3-NH3
17/20
Borohydride-amide materials
TGA
DSC
100
20
LiBH4 + Mg(NH2)2
90
22%
-20
100
9.1%
95
0
-20
Mg(BH4)2 + LiNH2
20
0
-20
Ca(BH4)2 + LiNH2
Mg(BH4)2 + LiNH2
Intensity [a.u.]
Mg(BH4)2 + LiNH2
Heat flow [mW]
Mass [% of starting mass]
9.5%
95
Ca(BH4)2 + LiNH2
Ca(BH4)2 + LiNH2
20
100
95
LiBH4 + Mg(NH2)2
20
100
90
LiBH4 + Mg(NH2)2
80
90
XRD
8.7%
Ca(BH4)2 + NaNH2
Ca(BH4)2 + NaNH2
0
-20
Ca(BH4)2 + NaNH2
90
100
200
300
400
500
Sample temperature [C]
600
100
200
300
400
500
600
Sample temperature [C]
20
40
Diffraction angle 2 []
Mixed borohydride-amide materials release hydrogen at low temperatures

Problems include poor reversibility and contamination of H2 with NH3
60
18/20
80
Path to improved reversibility

Approaches to new complex metal hydrides with improved hydrogen storage characteristics:
Selection of appropriate destabilizing agents to tune the stability of the intermediate species
and render them susceptible to dehydrogenation and rehydrogenation reactions.
Partial substitution of alkali or alkaline-earth cations with more electronegative cations (e.g.
transition metals) to achieve a more efficient electron delocalization and decrease stability.
Prediction and evaluation of new materials using

computational tools.
Synthesis and testing of promising predicted materials.
Identification of intermediate compounds formed during
dehydrogenation / rehydrogenation.
Optimization of the cycling characteristics using
destabilizing approaches and catalysis.
Criteria: Gravimetric and volumetric densities, equilibrium
pressure and temperature, fast dehydrogenation and
rehydrogenation reactions
19/20
Acknowledgements
Sandia National Laboratories:
Jay Keller, Marcina Moreno, Mark Allendorf, Eric Majzoub, Weifang Luo, Joe
Cordaro, Mitch Anstey, Ewa Rnnebro (currently at PNNL), Ethan Hecht,
Dennis Morrison, George Sartor, Ken Stewart
Metal Hydride Center of Excellence:

Craig Jensen (UH), John Vajo (HRL), Zak Fang (U. Utah), Channing Ann
(Caltech), Joseph Reiter (JPL), Jason Zan (JPL), J.-C. Zhao (OSU), John Vajo
(HRL), Dan Mosher (UTRC)
Financial Support:
U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy
under the Hydrogen Storage Grand Challenge, Metal Hydride Center of
Excellence (MHCoE) within DOE's National Hydrogen Storage Project
20/20

Complex Metal Hydrides For Reversible Hydrogen Storage: Vitalie Stavila

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Complex metal hydrides for

reversible hydrogen storage

Energy Storage Workshop, Santa Clara, CA, April 29, 2010

Hydrogen gas has almost three

No natural source of hydrogen;

Solid-state hydrogen storage, Ed. G. Walker, 2008.

Energy Storage Workshop, Santa Clara, CA, April 29, 2010

Hydrogen for transportation

Schlapbach & Zttel, Nature, 2001, 296.

Energy Storage Workshop, Santa Clara, CA, April 29, 2010