Complex Hydride Compounds with Enhanced Hydrogen …X. Tang & D. A. Mosher United Technologies...
Transcript of Complex Hydride Compounds with Enhanced Hydrogen …X. Tang & D. A. Mosher United Technologies...
1United Technologies Research Center
Complex Hydride Compounds with Enhanced Hydrogen Storage Capacity
S. M. Opalka, D. L. Anton,X. Tang & D. A. Mosher
United Technologies Research CenterE. Hartford, CT
R. ZidanT. Motyka
Savannah River National Laboratory
Aiken, SC
J. StricklerF.-J. Wu
Albemarle Corp.Baton Rough, LA
B. C. HaubackH. W. BrinksO. L. Martin
Institute for EnergyKjeller, Norway
C. QiuG. B. OlsonQuesTek, LLC/Northwestern U.
Evanston, IL
2005 DOE Hydrogen Program ReviewMay 23-26, 2005
Arlington, VAProject ID # ST6
This presentation does not contain proprietary or confidential information
2United Technologies Research Center
Overview• Timeline
– 11/30/02 Start– 12/31/06 End– 40% Complete
• Budget– $2.9 M Total Program
• $2.1M DoE• $0.8M (27%) UTC/ALB
– $0.43M DoE FY’04– $0.68M DoE FY’05
• Barriers– Gravimetric Density: 2 kWh/kg– Volumetric Density: 1.5 kWh/l– Charging rate: 1.5 kgH2/min.– Discharging rate: 4 gH2/sec.– Safety: Meets or exceeds
applicable standards– Durability: 1000 cycles
• Partners– SRNL– Albemarle
– IFE– QuesTek LLC
3United Technologies Research Center
ObjectivesTotal Program ObjectivesTo develop new complex hydride compounds that can:-Reversibly store > 7.5 weight % capacity, -Discharge H2 at rates required for PEM fuel cell operation, -Recharge for 1000 cycles with 100 % recovery.
First Year (2004) Objectives-Implement and validate new atomic-thermodynamic predictive methods.-Search out quaternary systems for high H capacity candidates formed from Na, Li, Ti, and/or Mg combined with Al and H, using multi-pronged approach:
Atomic-Thermodynamic ModelingSolid State Processing (SSP)
Molten State Processing (MSP)Solution Based Processing (SBP)
4United Technologies Research Center
Approach Virtual and Experimental Processing Methods
Solution Based Processing, SBP (Albemarle)- Excellent control- High purity products- Expensive processing- Cost- effective high
volume production
Molten State Processing, MSP (SRNL)- Rapid screening
- Wide range of T & P
- Includes metastable
phases
- Expensive equipment
Solid State Processing, SSP (UTRC)- Very rapid, low cost
screening- Limited conditions- High cost for high
volume production
Atomic-Thermodynamic Modeling (UTRC)- Survey broad
compositional spaces - Supplement
thermodynamic data- Generate descriptions
of phase behavior
Discover reversible high H compounds, AkxAeyM+iz(AlH4)(x+2y+iz), formed
between alkali (Ak) and alkaline earth (Ae) hydrides, metals (M), AlH3, and H2.
Unique aspect of approach: utilize a wide range of modeling and synthesis methods to search out and discover new high H2 capacity systems.
5United Technologies Research CenterCoupled methodologies provide the capability to discover and evaluate high H
capacity candidates’ thermodynamic phase behavior, prior to experimentation.
Accomplishments:Established Atomic-Thermodynamic Flowpath
Computational ThermodynamicsAssessment / database development
Direct Method Lattice DynamicsFinite temperature thermodynamic predictions
Density Functional Theory (DFT)Ground state (0 K) structures & enthalpies
INPUT: High H candidate phases
OUTPUT: Multi-order phase diagram & property predictions
Candidates with competitive ∆Hform(0 K)
Favorable candidates ∆Gform (298 K)
6United Technologies Research CenterValidation with experiment: lattice dynamic predictions in excellent agreement
with thermodynamic assessment of experimental Na alanate dissociation data.
Accomplishments:Validation of First Principles (FP) Predictions
10-1
100
101
102
103
PH
2, atm
1.5 2.0 2.5 3.0 3.5
1000/T(K)
Dymova 1974D
undoped NaAlH4(liq)
undoped Na3AlH6
NaAlH
NaAlH44 →→
1/3Na
1/3Na33 AlHAlH
66 ((αα)+2/3Al+H
)+2/3Al+H22
NaNa33 AlHAlH
66 ((αα))→→3NaH+Al+1.5H
3NaH+Al+1.5H22
NaNa33 AlHAlH
66 ((ββ))
Thomas 1999T
Ti-doped NaAlH4
Ti-doped Na3AlH6
Gross 2002G
Ti-doped NaAlH4
Bogdanovic 1997: PCIB
Ti-doped NaAlH4
Na3AlH6 from Ti-doped NaAlH4
Ti-doped Na3AlH6
Bogdanovic 2000: PCIB
Ti-doped NaAlH4
Na3AlH6 from Ti-doped NaAlH4
Bogdanovic 2000: dissociationB
Ti-doped NaAlH4
Ti-doped Na3AlH6
Lattice Dynamics PredictionThermodynamic Assessment
Dymova 1974Dymova 1974
undoped NaAlH undoped NaAlH44(liq)(liq)
undoped Na undoped Na33AlHAlH66
NaAlH4 →
1/3Na3 AlH
6 (α)+2/3Al+H2
Na3 AlH
6 (α)→3NaH+Al+1.5H
2
Na3 AlH
6 (β)
Thomas 1999Thomas 1999
Ti-doped NaAlH Ti-doped NaAlH44
Ti-doped Na Ti-doped Na33AlHAlH66
Gross 2002Gross 2002
Ti-doped NaAlH Ti-doped NaAlH44
Bogdanovic 1997: PCIBogdanovic 1997: PCI
Ti-doped NaAlH Ti-doped NaAlH44
Na Na33AlHAlH66 from Ti-doped NaAlH from Ti-doped NaA 4
Ti-doped Na Ti-doped Na33AlHAlH66
Bogdanovic 2000: PCIBogdanovic 2000: PCI
Ti-doped NaAlH Ti-doped NaAlH44
Na Na33AlHAlH66 from Ti-doped NaAlH from Ti-doped NaA 4
Bogdanovic 2000: dissociationBogdanovic 2000: dissociation
Ti-doped NaAlH Ti-doped NaAlH44
Ti-doped Na Ti-doped Na33AlHAlH66
Experimental Data
7United Technologies Research Center
Accomplishments:Integrated Experimental & FP Predicted Data
Predictions extend computational thermodynamics beyond experimental realm. Phase diagrams calculated from integrated assessment of experimental data and predictions used to evaluate candidate phase stability over a wide range of T & P.
10-12
10-10
10-8
10-6
10-4
10-2
100
102
104
106
108
PH
2, atm
0.8 1.2 1.6 2.0 2.4 2.8 3.2 3.6
1000/T(K)
liq(NaH)liq(NaH)
liq(Na)liq(Na)
bcc(Na)bcc(Na)
NaHNaH
NaAlHNaAlH44
αα-Na-Na33AlHAlH
66
ββ-Na-Na33AlHAlH
66
←←
10-1
100
101
102
103
104
105
PH
2, atm
0 5 10 15 20 25
Al, at.%
NaH+fcc(Al)NaH+fcc(Al)
αα-Na-Na33AlHAlH66+fcc(Al)+fcc(Al)
NaAlHNaAlH44+fcc(Al)+fcc(Al)
<--NaH<--NaH
<--liquid<--liquid
αα-N
a-N
a 33AlH
AlH
66
NaA
lHN
aAlH
44
Potential diagram 100oC Isothermal phase section100oC
8United Technologies Research Center
Accomplishments:Virtually Surveyed Multiple Quaternary Spaces
AlNa
Ti
H
TiH2
AlH3
NaH Na3AlH6
NaAlH4
TiH2-xTi3Al
Al2Ti
Al3Ti
Aerial View of Na-Ti-Al-H Quaternary Pyramid
Year II Quaternary Systems:To Date:Na-Mg-Al-HLi-Mg-Al-HSurveyed >40 Phases to dateIdentified Numerous Candidates!
Year I Quaternary Systems:Na-Ti-Al-HLi -Ti-Al-HNa-Li-Al-HSurveyed >170 PhasesNo Candidates Found!
FP atomic-thermodynamic methodologies used to accelerate survey of broad compositional phase spaces, reducing and focusing experimental effort.
High Capacity Media Criteria:7.5 wt% retrievable H capacityStability ∆Gformation<< O∆Gdehydrogenation O
BCCNa/Ti
Phases Simulated:Complex hydridesCompeting phasesLower order phasesHypothetical End-
Members
9United Technologies Research Center
Accomplishments:Integrated Predictions and Experiments
Successfully employed FP predictions to evaluate Na2LiAlH6 structure and phase behavior. Explained observed synthesis and disproportionation reactions.
Na2LiAlH6 Reactions
0.010.1
110
1001000
10000
200 300 400 500 600
T (K)
K (e
quil.
con
stan
t) o
r P (a
tm)
4/3NaAlH4+2/3LiH <=> 2/3Na2LiAlH6+2/3Al+H2
2/3Na2LiAlH6 <=> 4/3NaH+2/3LiH+2/3Al+H2
2/3LiAlH4+4/3NaH <=> 2/3Na2LiAlH6
2/9Li3AlH6+4/9Na3AlH6 <=> 2/3Na2LiAlH6Na2LiAlH6 P21/cStable Low T StructureID from Collaboration
First two reactions correspond to a 2-step 5.2 w/o H2 reversible system.
1st, 3rd & 4th reactions for synthesis.
Dissociation Pressure/ Mole H2 Released
NaAl H4 = 1/3Na3AlH6+2/3Al+H2
2/3Na3AlH6=2NaH+2/3Al+H2
0.0010.01
0.11
10100
1000
0.0015 0.002 0.0025 0.003 0.00351/T (K)
P (a
tm)
Predicted and experimental (Fossdal et. al, J. Alloys Compd., in press.)dissociation P are in excellent agreement.
100oC
2/3Na2LiAlH64/3NaH+2/3LiH+2/3Al+H2
∆H = 52.4kJ/Mol
NaAlH41/3Na3AlH6+2/3Al+H2
2/3Na3AlH6 2NaH+2/3Al+H2
4/3NaAlH4+2/3LiH 2/3Na2LiAlH6+2/3Al+H22/3Na2LiAlH6
4/3NaH+2/3LiH+2/3Al+H22/3LiAlH4+4/3NaH 2/3Na2LiAlH62/9Li3AlH6+4/9Na3AlH6
2/3Na2LiAlH6
10United Technologies Research Center
Accomplishments:Identification of High Capacity Candidates
Atomic Structure
LiMgAlH6 Candidate
Combined predictive methodologies are effective in identifying and evaluating new candidate hydrides, yielding recommendations for experimental evaluation.
Some Proposed LiMgAlH6 Disproportionation Reactions
0.11
10100
100010000
100000
0.001 0.0015 0.002 0.0025 0.003 0.0035
1/T(K)
Dis
soci
atio
n Pr
essu
re (a
tm)
Some Proposed LiMgAlH6 Disproportionation Reactions
0.11
10100
100010000
100000
0.001 0.0015 0.002 0.0025 0.003 0.0035
1/T(K)
Dis
soci
atio
n Pr
essu
re (a
tm)
2/3 (LiMgAlH6 <=> LiH+MgH2+Al+3/2H2) 4.7w/o H2
(17LiMgAlH6 17LiH+Al12Mg17+5Al+42.5H2)/42.5 7.9 w/o H2
100oCNumerous possible disproportionation products are currently being evaluated. Actual reversible H2 content dependent upon identification of most favorable dehydrogenation end products.
Many mixed alkali/alkaline earth alanate candidates
predicted to have ∆Hform (0 K)>-8 kJ/mol*atom
11United Technologies Research Center
AccomplishmentsNew High H Capacity Material Search Strategy
A method of predicting destabilized alanate compounds with in-siturechargeability can be described thermodynamically as:
M1(AlH4)y + M2Hx <=> M1M2Hi + Al + (4y+x-i)/2H2
where:∆G ~ 0 ~ Gf
oM1M2Hi + Gf
oAl + RTln(PH2) – Gf
oM1(AlH4)y – Gf
oM2Hx
Systematic Approach: -Comprehensively search databases to select candidates from known phases.
-Identify candidate phase chemical reactions, prioritize according to H2 storage capacity.
-Where thermodynamic data is unavailable, predict thermochemical properties.
-Conduct thermodynamic assessments combining both experimental and predicted data
to evaluate in-situ reversibility for hydrogen storage.
at 70<T<120oC & 1<P<100 bar and M1 & M2 are metal ions.
New modeling tools used to select candidates for focused synthetic evaluation.
12United Technologies Research Center
AccomplishmentsNew Hydrogen Storage Opportunities
1.E-03
1.E-02
1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
2 2.2 2.4 2.6 2.8 3 3.2 3.4
1000/TPr
essu
re
• All in-situ rechargeable systems have ∆Hf ≈ 40 kJ/mole H2.• ∆Hf ≈ 0 kJ/mole H2 reactions can only be achieved at ~106 bar.• This results from ∆Sf for MHx approximately constant.
2LiBH4 + MgH2 MgB2 +2LiH + 4H2* 11.4 w/o H260
ord
ers
o f m
a gni
t ud e
in P
H2
1.E-30
1.E-27
1.E-24
1.E-21
1.E-18
1.E-15
1.E-12
1.E-09
1.E-06
1.E-03
1.E+00
1.E+03
1.E+06
1.E+09
1.E+12
1.E+15
1.E+18
1.E+21
1.E+24
1.E+27
1.E+30
0 0.5 1 1.5 2 2.5 3 3.5 4
1000/T
Pres
sure
2H(g) H2(g)
H2O(g) H2(g) + O2(g)
6 or
d er s
of m
agn i
tude
in P
H2
In-situ windowof reversibility
25<T<120oC1<P<100 bar
Complete Range of Systems Near Reversible SystemsMgH2+ Si Mg2Si+H2
* 5.0 w/o H2
H2O(g) H2(g) + O2(g)
2H(g) H2(g)
** Vajo et. al, MRS (2004)1000/T 1000/T
Thermodynamic assessments of in-situ reversible hydrogen storage reactions.
13United Technologies Research Center
Al
Na
AlH6
H2
AlH3
NaH2
Al
Na Tm
NaAlH4
Na3AlH6
H
AlH
NaH
TmH
1:1:1Na:Tm:Al
Na:Ti:AlNa:Li:Al
Na:Mg:AlNa:Ti:Li:Al
Na:Ti:Mg:AlNa:Li:Mg:Al
Li:Mg:Al
Am/Ae/Tm
25 30 35 40 45 50 550
400
60 65 70 75 80 85Two-Theta (deg)
0
400
62-3324> Al - Aluminum62-1323> Halite - Na Cl
62-9625> Ti H2 - Titanium Hydride (1/2) - Ht60-7922> Na (Al H4) - Sodium Tetrahydridoaluminate
42-0786> AlH6Na3 - Sodium Aluminum Hydride60-1644> Na Al Cl4 - Sodium Tetrachloroaluminate
Inte
nsity
(CPS
)
74.5 wt% NaCl, 150A, RIR = 4.879.9 wt% TiH2, 99A, RIR = 7.497.0 wt% Al, 59A, RIR = 4.455.9 wt% Na3AlH6, Hi T, 227A, RIR = 1.52, est.2.8 wt% NaAlH4, 505A, RIR = 2.81
possible trace of NaAlCl4
WPF
theta calBkd & Ka2 Subtd 38.8o
NaAlCl4
NaCl
Na3AlH6NaAlH4
TiH2Al
NaCl
NaCl
NaCl NaCl NaClNaCl
TiH2
TiH2 TiH2
Na3AlH6
Processing• Hand Mix XRD• SPEX Mill 3 hr. XRD• 200barH2/60oC/20 hr XRD• 200barH2/80oC/20 hr XRD• 200barH2/100oC/20 hr XRD• 200barH2/120oC/20 hr XRD
AnalysisSemi-quantitative analysis using:
MDI Corp. Jade 7.0utilizing data bases:
ICDD/PDF-2 Release 2002ICSD Release 2004/2.
AccomplishmentsSolid State Processing (SSP) System Surveys
High throughput SSP screening of 7 quaternary/quinary systems completed.
14United Technologies Research Center
NaH:TiCl2:AlH3 = 3:1:1
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
3hrs. 60oC/200bar/20hrs 80oC/200bar/20hrs 100oC/200bar/20hrs 120oC/200bar/20hrs
Aim Composition Hand Mixed SPEX Milled Charged Charged Charged Charged
Mol
ecul
ar %
NaClAlNaTiH1.924TiH1.5b-Na3AlH6a-Na3AlH6NaAlH4AlH3TiCl2NaHTiCl2 signal is absorbed
2NaH + TiCl2 + AlH3 -> 2NaCl + TiH2 + Al + 5/2 H2
The most effective method was to add cations as hydride species. This method readily produced NaAlH4 upon SPEX milling.
No previously unidentified phases found in the Na-Li-Ti-Al-H systems.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
3hrs. 60oC/200bar/20hrs 80oC/200bar/20hrs 100oC/200bar/20hrs 120oC/200bar/20hrs
Aim Composition Hand Mixed SPEX Milled Charged Charged Charged Charged
Mol
ecul
ar %
Na
TiH1.924
TiH1.5
b-Na3AlH6
a-Na3AlH6
NaAlH4
Al
Ti
NaH
slight absorption of
NaH by Ti
reduction of Na & generation of
TiH1.5
hydrogenation of Ti,hydrogenation of Na, generation of TiH1.9 &
generation of significant β-Na3AlH6
generation of NaAlH4
NaH + Ti + Al + H2 => NaAlH4 + TiHx
3NaH + Ti + Al + H2 => Na3AlH6 + TiHx
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
3hrs. 60oC/200bar/20hrs 80oC/200bar/20hrs 100oC/200bar/20hrs 120oC/200bar/20hrs
Aim Composition Hand Mixed* SPEX Milled Charged Charged Charged Charged
Mol
ecul
ar %
Al
NaAlH4AlH3
TiH2NaH
NaH +TiH2 + AlH3 => TiH2 + NaAlH4
NaH:TiCl2:Al
NaH:Ti:Al
NaH:TiH2:AlH3
Cations introduced via chloride additions led to far too much MClx to be effective.
Primary metal additions were only an effective method of synthesizing NaxAlHy at temperatures > 100oC.
AccomplishmentsDevelopment of SSP NaH:TiH2:AlH3 Method
NaH+TiH2+AlH3 => TiH2+NaAlH4
2NaH+TiCl2+AlH3=>2NaCl+TiH2+Al+3/2H2
NaH+Ti+Al+5/2H2 => NaAlH4+TiHx
3NaH+Ti+Al+5/2H2 => Na3AlH6+TiHx
15United Technologies Research Center
XRD Analysis of Constituent PhasesCAP04-031
LiH:MgH2:AlH3 = 1:1:1
0%
20%
40%
60%
80%
100%
3hrs. 60oC/200bar/20hrs 80oC/200bar/20hrs 100oC/200bar/20hrs 120oC/200bar/20hrs
Aim Composition Hand Mixed* SPEX Milled Charged Charged Charged Charged
Mol
ecul
ar %
Al2Li3MgLi3AlH6LiAlH4NaMgH3AlNaAlH4AlH3MgH2LiH
LiH + MgH2 + AlH3 => 2/3Al + MgH2 + 1/3Li3AlH6
LiH + MgH2 + AlH3 => LiH + MgH2 + AlLi3AlH6 <=> 3LiH + Al + 3/2H2
5.6wt% 80<T<100oC
unidentified peaks at 9.5 & 30o
at 80oC
LiH + MgH2 + AlH3 => MgH2 + LiAlH4
LiH:MgH2:AlH3
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
3hrs. 60oC/200bar/20hrs 80oC/200bar/20hrs 100oC/200bar/20hrs 120oC/200bar/20hrs
Aim Composition Hand Mixed* SPEX Milled Charged Charged Charged Charged
Mol
ecul
ar %
LiNa2AlH6NaAlH4 (L2q)AlAlH3TiH2LiHNaH
NaH + LiH + TiH2 + AlH3 => TiH2 + 1/3NaAlH4 + 1/3Al + 1/3LiNa2AlH6 + 2/3Li?
NaH + LiH + TiH2 + AlH3 => TiH2 + 1/2Al + 1/2LiNa2AlH6 + 1/2Li?
2NaAlH4 + LiH <=> LiNa2AlH6 + Al + 3/2H2 2.6w/o
NaH:TiH2:LiH:AlH3
0%
20%
40%
60%
80%
100%
3hrs. 60oC/200bar/20hrs 80oC/200bar/20hrs 100oC/200bar/20hrs 120oC/200bar/20hrs
Aim Composition Hand Mixed* SPEX Milled Charged Charged Charged Charged
Mol
ecul
ar %
NaMgH3NaAlH4 (L2q)AlAlH3TiH2MgH2NaH
NaH + MgH2 + TiH2 + AlH3 => MgH2 + TiH2 + NaAlH4
NaH + MgH2 + TiH2 + AlH3 => 1/2MgH2 + TiH2 + 1/2NaAlH4 + 1/2NaMgH3 + 1/2Al
NaAlH4 + MgH2 <=> NaMgH3 + Al + 3/2H2 3.7wt%
NaH:MgH2:TiH2:AlH3
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
3hrs. 60oC/200bar/20hrs 80oC/200bar/20hrs 100oC/200bar/20hrs 120oC/200bar/20hrs
Aim Composition Hand Mixed* SPEX Milled Charged Charged Charged Charged
Mol
ecul
ar %
LiNa2AlH6NaMgH3NaAlH4 (L2q)AlAlH3LiHMgH2NaH
NaH + MgH2 + LiH + AlH3 => 3/4MgH2 + 1/8LiNa2AlH2 + 1/2NaAlH4 + 1/4NaMgH3 + 3/8Al
NaH + MgH2 + LiH + AlH3 => 3/4MgH2 + 3/8LiNa2AlH6 + 1/4NaMgH3 + 1/2Al + 5/8LiH(?)
LiH absrobed
4NaAlH4 + LiH + 2MgH2 <=> LiNa2AlH6 + 2NaMgH3 + 3Al + 5H2 3.99wt%
AccomplishmentsSSP NaH-LiH:MgH2:TiH2:AlH3 System Survey
NaH:MgH2:LiH:AlH3
NaAlH4+MgH2 NaMgH3+Al+3/2H2 3.7 w/o4NaAlH4+LiH+2MgH2
Na2LiAlH6+2NaMgH3+3Al+9/2H2 3.3 w/o
2NaAlH4+LiH Na2LiAlH6+Al+3/2H2 2.6 w/o Li3AlH6 3LiH + Al+3/2H2 5.6 w/o
Numerous mixed compound systems identified having H2 capacities ranging from 2.6-5.6 w/o, and which are rechargeable ≤ 200 bar at T<120oC.
16United Technologies Research Center
20 30 40 50 60x10^3
2.0
4.0
6.0
8.0
10.0
70 80 90 100 110 120Two-Theta (deg)
x10^3
2.0
4.0
6.0
8.0
10.0
[05-080.MDI] CAP05-004k,0.065gLiH,).21gMgH2,0.48gNi,0.24gAlH3,SPX3h,Chg100C,190b,20h <Psi97-003-7756> Nickel - Ni97-002-1490> Mg H2 - Magnesium Hydride97-003-3329> Al - Aluminum97-007-6165> Li3 Al D6 - Trilithium Aluminium Deuteride
Inte
nsity
(Cou
nts)
theta cal
Bkd & Ka2 Subtd
59.5 w% Ni, 317A, RIR = 8.15, shi-0.01416.6 w% MgH2, 166A, RIR = 2.73, shi+0.00720.4 w% Al, 364A, RIR = 4.47, shi-0.0093.5 w% Li3AlH6, 412A, RIR = 0.96, shi-0.135
R/E = 2.60
Al
AlH6
H2
AlH3
NaH
Al
Am Tm
NaAlH4
Na3
AlH6
H
TmAl3
NaH
TmAl
Tm3Al
CY ‘04:Hand Mix, Ball Mill60, 80, 100 & 120oC
/200bar/20 hrsCY ’05:Hand Mix, Ball Mill100oC/200bar/20 hrs
Li:Ni:AlNa:Ni:AlMg:Ni:Al
Li:Mg:Ni:AlNa:Mg:Ni:Al
Li:Co:Al
Ak/Ae/Tm
Na:Co:AlMg:Co:Al
Na:Mg:Co:AlLi:Fe:AlNa:Fe:AlMg:Fe:Al
Mg2NiH4Mg2CoH5Mg2FeH6
Li2Mg(NiH4)2Na2Mg(CoH5)2LiNaMg(FeH6)2
?
1:1:1Am/Ae:Tm:Al
• Moving on to transition metal substituted systems.• Maximize compositional ranges covered by using fewer thermal treatments.
AccomplishmentsSSP 2005 Approach Going Forward
17United Technologies Research Center
20 30 40 50 60 70 80 90
NaHLiHNaAlH4
Na3AlH6
Na2LiAlH6
Tape TSS Holder sUnidentif. ?
s
s
T
T
?
NaH + LiH +NaAlH4 =>Na2LiAlH6 Range ofProcessing Conditions
RT-600oC200 bar
8 hr dwell timeQuiescent or agitated1 liter ~600g capacity
Demonstrated MSP advantages: Solvent- and anion-free processing produces high yields of clean complex hydrides. One liter pressure vessel scaleable to meet system demonstration requirements.
Processing Conditions190oC, 200 bar, 15 min. dwell time, agitated
AccomplishmentsMolten State Processing (MSP) Proof of Concept
18United Technologies Research Center
AccomplishmentsMSP Compositional System Surveys
10 20 30 40 50 60 70 80Two-Theta (deg)
0
500
1000
1500
2000
2500
3000
Inte
nsity
(Cou
nts)
[lump.xrdml] NaKLiAlH6 #189-2778> KH - Potassium Hydride
43-1437> KAlH4 - Potassium Aluminum Hydride76-0172> NaH - Sodium Hydride
42-0848> AlH6LiNa2 - Lithium Sodium Aluminum Hydride42-0786> AlH6Na3 - Sodium Aluminum Hydride
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[lump.xrdml] NaKLiAlH6 #189-2778> KH - Potassium Hydride
43-1437> KAlH4 - Potassium Aluminum Hydride76-0172> NaH - Sodium Hydride
42-0848> AlH6LiNa2 - Lithium Sodium Aluminum Hydride42-0786> AlH6Na3 - Sodium Aluminum Hydride
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[20050113-001.xrdml] Mg, SAH Introducing Mg01-070-3873> NaMgH3 - Sodium Magnesium Hydride
03-065-2869> Al - Aluminum01-089-5003> Mg - Magnesium
01-074-0934> MgH2 - Magnesium Hydride01-073-0088> NaAlH4 - Sodium Aluminum Hydride
01-077-2064> NaCl - Sodium Chloride
30 40 50 60 70 8030 40 50 60 70 80Two-Theta (deg)
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[20050113-001.xrdml] Mg, SAH Introducing Mg01-070-3873> NaMgH3 - Sodium Magnesium Hydride
03-065-2869> Al - Aluminum01-089-5003> Mg - Magnesium
01-074-0934> MgH2 - Magnesium Hydride01-073-0088> NaAlH4 - Sodium Aluminum Hydride
01-077-2064> NaCl - Sodium Chloride
NaAlH4+LiH+KH=> LiNa2AlH6+KAlH4+NaH+KH+Na3AlH6+ ?
Processing Conditions
NaAlH4+MgH2=> Al+NaMgH3+Mg
190oC, 200 bar, 15 min. dwell time, agitatedProcessing Conditions
190oC, 200 bar, 15 min. dwell time, agitated
Multiple unidentified peaks
identified
Four quaternary/quinary composition systems investigated to date:Na-Li-Al-HNa-Ti-Al-H Na-K-Li-Al-HNa-Mg-Al-H
89-2778> KH - Potassium Hydride43-1437> KAlH4 - Potassium Aluminum Hydride
76-0172> NaH - Sodium Hydride42-0848> AlH6LiNa2 - Lithium Sodium Aluminum Hydride
42-0786> AlH6Na3 - Sodium Aluminum Hydride
89-2778> KH - Potassium Hydride43-1437> KAlH4 - Potassium Aluminum Hydride
76-0172> NaH - Sodium Hydride42-0848> AlH6LiNa2 - Lithium Sodium Aluminum Hydride
42-0786> AlH6Na3 - Sodium Aluminum Hydride
NaMgH3 - Sodium Magnesium Hydrid03-065-2869> Al - Aluminum
01-089-5003> Mg - Magnesium01-074-0934> MgH2 - Magnesium Hydrid
01-073-0088> NaAlH4 - Sodium Aluminum Hydride01-077-2064> NaCl - Sodium Chloride
NaMgH3 - Sodium Magnesium Hydrid03-065-2869> Al - Aluminum
01-089-5003> Mg - Magnesium01-074-0934> MgH2 - Magnesium Hydrid
01-073-0088> NaAlH4 - Sodium Aluminum Hydride01-077-2064> NaCl - Sodium Chloride
Multiple unidentified peaks observed in Na:Li:K:Al:H system provided evidence for formation of new compounds.
19United Technologies Research Center
After Fusion At 200 bar, 190oC,15 min.
TPD discharge experiments showed MSP hydrides to be more active than conventionally ball milled hydrides. This material is being kinetically examined for possible use in CCHSS#2.
Before FusionSolid-state processed NaAlH4 + 4%TiH2
AccomplishmentsMSP Produced Highly Active NaAlH4
20United Technologies Research Center
AccomplishmentsSolution Based Processing (SBP) Ti/Na Alanates
2%Ti+3
4%Ti+3
10%Ti+3
NaAlH4
NaAlH4
NaAlH4 Na3AlH6
Na3AlH6
Al
Al/Al3Ti
NaClNaClNaCl
NaCl
NaAlH4
NaAlH4NaAlH4
NaAlH4
NaAlH4
Al/Al3Ti
TiCl4(THF)2 + Al(i-Bu)3 TiCl3(THF)3NaAlH4 + xTiCl3(THF)3 NaTixAl1-xH4 + ….
Mole ratioTi:Al
2:100 4:100 10:100 33:100
Mole ratioH2:Ti
7.7 6.7 6.4 5.7
NaTixAl1-xH4xAl3Ti + 6xH2 + (1-3x)NaAlH4
Hydrogen Evolution as a Function of Time and Temperature
050
100150200250300350400450500
0 20 40 60 80 100 120 140
Time (min.)
H 2 E
volu
tion
(ml)
-10
-5
0
5
10
15
20
25
Tem
pera
ture
(deg
C)
2% Ti+3
•Complete solution doping reaction at 25oC.•Disproportionation to Al3Ti.•New ordered phases observed in related systems.
Demonstrated SBP synthesis route to homogeneous Ti+3 doped alanates. This material is being kinetically examined for possible use in CCHSS#2.
21United Technologies Research Center
Future Work
FY’05 Deploy integrated methods to search and discover high capacity systems.FY’06 Refine new system compositions. Catalyze improved kinetic performance.
Thermodynamics Survey of Compositional Space
Phase Behavior PredictionsFY’05 Designed Endproducts
FP ModelingNew Phase Simulations
Thermodynamic PredictionsFY’05 Ak/Ae with Al, B & TM
ExperimentationSynthesis, Characterization,
Performance Evaluation
New phase structures
ID systems withcompetitive stability
Discovery of High H Capacity Hydrides
Discovery of High H Coupled Reactions
ID compositional targets
Recommendsyntheses
Solution Based ProcessingNew Phases from Chemical
Design and SynthesisFY’05 Ak/Ae with Al, B & TM
Solid State ProcessingNew Phases from
Mechanochemical MixingFY’05 Ak/Ae with Ni, Co, Fe
Molten State ProcessingNew Phases fromHigh T & P Fusion
FY’05 Ak/Ae with V, Cr, Mn
Parallel Search Strategies
New phase properties
Validate predictionsRefine compositionsRefine
compositions
Ak = alkaliAe = alkaline earthTM = transition metals
22United Technologies Research Center
Responses to Previous Year Reviewers’ Comments
• Comment“Consider broadening to include non-alanate materials?”By adding other complexing elements such as B, Ga … vastly increases the scope of investigation, thus limiting empirical investigations into all possible combinations. Additions of these elements will be investigated atomistically and empirically where modeling indicates high hydrogen capacity materials are stable.
• Comment“DOE should consider how this project relates to or coordinates with the Sandia Metal Hydride Center of Excellence?”UTRC has always maintained a high degree of communication with SNL and many of its CoE partners through DoE sponsored meetings, IEA meetings, and laboratory visits. This communication will continue.
• Comment– “Need validation that the modeling is predicting properties correctly.”– “Need to insure that the modeling efforts are not independent of experiment.”
As shown in the progress to date, modeling and empirical results have shown very good agreement. We have a very high confidence level in modeling predictions when phonon approach is incorporated. The modeling & empirical efforts are designed to be interdependent with each other, and are closely coordinated with monthly meetings used to exchange data, ideas, and concepts.
23United Technologies Research Center
Backup Slides
24United Technologies Research Center
O. M. Løvvik, S. M. Opalka, H. W. Brinks, and B. C. Hauback, “Crystal structure and thermodynamic stability of the lithium alanates LiAlH4 and Li3AlH6,” Phys. Rev. B 69 134117-134125 (2004).
H.W. Brinks, B.C. Hauback, C.M. Jensen, and R. Zidan, “Synthesis and crystal structure of Na2LiAlD6,” J. Alloys Compd. 392(1-2) 27-30 (2005).
O. M. Lovvik and S. M. Opalka, “First-principles calculations of Ti-enhanced NaAlH4,” Phys. Rev. B 71 054103-1-10 (2005).
O. M. Lovvik, O. Swang, and S. M. Opalka, “Modeling alkali alanates for hydrogen storage by density-functional band-structure calculations” submitted 4/05 J. Mater. Res.
C. Qiu, S. M. Opalka, G. B. Olson, and D. L. Anton, “The Na-H System: from First Principles Calculations to Thermodynamic Modeling,” submitted 4/05 Phys. Rev. B. Two related papers on the Na-Al-H and Na-Ti-Al-H system currently in preparation.
Presentations
Publications
O. M. Løvvik and S. M. Opalka, “First-principles calculations of Ti-enhanced NaAlH4.” International Symposium of Metal Hydrogen Systems (MH2004), Cracow, Poland, September 10, 2004.
R. Zidan, “Development and Characterization of Complex Hydrides,” Invited Speaker, ASM Material Solution Conference, Columbus, OH, Oct. 18-21, 2004.
R. Zidan, “Hydrogen Storage R&D Key Issues for the Hydrogen Economy,” and “Solid-State Hydrogen Storage Systems,”Hydrogen Economy Workshop, Invited Speaker as Representative for the Department of Energy, Cairo, Egypt, January 31 –February 2, 2005.
C. Qiu, S. M. Opalka, D. L. Anton, and G. B. Olson, “Thermodynamic Modeling of Sodium Alanates,” Materials Science & Technology 2005, to be held in Pittsburgh, PA, on September 25-28, 2005.
S. M. Opalka, O. M. Lovvik, H. W. Brinks, B. C. Hauback, and D. L. Anton, “Combined Experimental-Theoretical Investigations of the Na-Li-Al-H System,” Materials Science & Technology 2005, to be held in Pittsburgh, PA, on September 25-28, 2005.
Multiple collaborations foster H2 storage research progress and communication.
25United Technologies Research Center
SafetyRisk Identification
DoE Hydrogen Storage Safety Review Committee use only not for public dissemination 1
Burn Rate Test
13.110
16.082.97
20.016.90
24.2011.09
Partially Discharged CCH#0-33
DoE Hydrogen Storage Safety Review Committee use only not for public dissemination 13
Water Immersion Test
4.120
4.23.11
4.24.12
4.27
Partially Discharged CCH#0-33
DoE Hydrogen Storage Safety Review Committee use only not for public dissemination 14
Water Injection31.06
031.200.14
31.230.17
1:01.0930.03
Partially Discharged CCH#0-33
DoE Hydrogen Storage Safety Review Committee use only not for public dissemination 17
Dust Explosion Testing
430584137.5137.5TcoC
17110<7<7MIE mJ
306590140MEC g/m3
St-1St-1St-3St-3Dust Class
139124326869Kst bar-m/s
51142612003202Rmax bar/s
7.47.38.911.9Pmax bar-g
Lycopodium Spores
Pitt. Seam Coal Dust
NaH+AlNaAlH4
Reference MaterialsTest Materials
Pmax = maximum explosion pressure, Rmax = pressure rise maximum, Kst = maximum scaled rate of pressure rise,MEC = minimum explosive concentration, MEI = minimum spark ignition energy, Tc = minimum dust cloud ignition temperature
•Dust explosion: class St-3, Highly Explosive when finely divided and dispersed.
Fire risk quantitatively
assessed
Explosion risks quantitatively
assessed
Appendix V- UTRC Risk Assessment Form Date Room Number Participants 5/4/04 S145H Tom Ververis, Xia Tang, Ron Brown, Jodi Vecchiarelli
No Process, Task or Step
Potential hazard
Controls in Place Likelihood Occurrence
Potential Impact
Risk Rank
Controls Required To reduce risk further/Name/Date
1 Mixing Powder Media Preparation
Fire, Explosion All work is done in glovebox filled with Nitrogen Containers inside glove box sealed Gloves inspected every day Nitrogen pressure checked every day Moisture and O2 sensor in glovebox Positive pressure maintained in glove box
2 3 6 Med
2 Hydrogen Storage Running Test
Failure of High Pressure Systems Fire, Explosion
Restricted use Risk assessments Local rules and procedures Pressure rated components Pressure relief valves Automatic controllers; Redundant valves Detailed Procedures; Employee training Critical valve Maintenance Remote gas line shutoff and purge if loss of power or ventilation All test stands in hoods All equipment leak tested (H2 sniffer) Flash arrestor Moisture filters
2 3 6 Med
Lower Pressure
3 Hydrogen Storage, Running Test
High Temp. Oil Bath, Burns, Oil spill
Warning sign “Hot Oil” Secondary containment Redesigned Jack stand gard in place Located in hood.
2 2 4 Low
4 Vacuum System (Hydrogen),Running Test
Explosion Special Hydrogen Vac. Pumps Sparkless
2 3 6 Med
5 Working in glovebox
Ergonomic pain Limited time in glovebox to 45 minutes max. Set up to avoid awkward reaching
2 2 4 Low
6 Lifting, transporting samples
Ergonomics Training, procedures Weight kept to < 30 pounds
2 2 4 Low
Comprehensive risk assessment performed on all major operations
quantitatively describing both impact and probability of occurrence.
26United Technologies Research Center
SafetyRisk Mitigation
Material handled under inert gas
Incoming material stored in fire cabinet
Materials tested in commercial equipment installed in a glove
box
Media stored under inert gas
All risks reduced to low impact or negligible probability.