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Hydrogen Storage
Ned T. Stetson
2010 Annual Merit Review and Peer Evaluation Meeting(8 June 2010)
2
Goal & Objectives
• System Engineering / Systems Analysis– Demonstrate the technologies required to achieve the 2015 DOE on-board
vehicle hydrogen storage goals– Continue storage system analysis/projections for advanced storage system
capabilities & development of system models for on-board storage systems– Increase emphasis on early market applications
• Continue R&D on materials for breakthrough storage technologies
– Continue new hydrogen storage material discovery R&D for advanced storage systems
– Strengthen coordination between basic & applied research within DOE and across agencies
Develop on-board storage systems that meet all DOE system targets simultaneously.
Goal: On-board hydrogen storage for > 300 mile driving range across different vehicle platforms, without compromising passenger/cargo space or performance
3
Budget
EMPHASIS
Systems approach through the Engineering CoE, in collaboration with independent materials development projects, to achieve light-duty vehicle targets
Continued close coordination with Basic Energy Science in 2010 & 2011 and improve coordination with National Science Foundation, Advanced Research Projects Agency - Energy, and Energy Frontier Research Centers activities
Focus on cost reduction for high pressure tanks
Increased analysis efforts for low to high production volumes
Increase emphasis on early market storage applications
FY 2010 Appropriation = $32.0MFY 2011 Request = $20.0M
$5.5
$4.3
$6.3
$0.9$0.5
$6.0
$8.3
$2.0
$0.8
$3.8
$1.1 $1.6
$2.4
$8.2
$0
$1
$2
$3
$4
$5
$6
$7
$8
$9
$M
FY10 Appropriation FY11 Request
Material Centers are being completed as planned at the end of Fiscal Year 2010
4
Challenges
Materials discovery research is still needed for long-term,
advanced materials with full set of properties for
materials-based hydrogen storage options!
TIAX 12/2009
1 Cost estimate in 2005 USD. Includes processing costs.
Compressed gas offers a near- term option, but cost is an issue
Compressed gas storage offers a near-term option for initial vehicle
commercialization and early markets
• Cost of composite tanks is challenging• > 75% of the cost is projected to be due to the
carbon fiber layer• Additional analysis is needed to better understand
costs at lower manufacturing volumes
Advanced materials development is still needed for long-term solutions
Progress in Storage Capacity
• Projections performed by Argonne National Laboratory using the best available materials data and engineering analysis at the time of modeling
• Analyses included for:• Physical storage – liquid, 350 & 700 bar compressed and cryo-compressed• Materials-based – reversible sorbents and metal hydrides and off-board
regenerable chemical hydrogen systems
In just five years of accelerated investment, DOE has made significant progress in near- and long-term approaches.
Projected Capacities for Complete 5.6-kg H2 Storage Systems
0
1
2
3
4
5
6
7
2005 2006 2007 2008 2009 2010
Year
Gra
vim
etric
Cap
acity
(Wt.%
)
2010 Target
2015 Target
0
10
20
30
40
50
2005 2006 2007 2008 2009 2010Year
Volu
met
ric C
apac
ity (g
-H2/
L)
2015 Target
2010 Target
Gravimetric Volumetric
However no one system is yet able to meet all targets simultaneously
6
Portfolio Management & Progress
Metal Hydrides More than 81 distinct material systems assessed experimentally—not including catalyst/additive studies
~ 75% discontinued~ 25% still being investigated
Computational/theoretical screening done on more than 20 million reaction conditions for metal hydrides
Chemical Hydrogen Storage> 130 materials/combinations have been examined~ 95% discontinued~ 5% still being investigated-Ammonia Borane (AB)
solid, ammonium borohydride, or mixture of AB with ionic liquids as liquid fuels
Hydrogen Sorption~ 210 materials investigated ~ 80% discontinued~ 20% still being investigated
Many new material systems have been investigated through the three Materials Centers of Excellence.
7
Hydrogen Storage Materials DatabaseA database has been created to capture materials data from the research projects
• Database is designed to capture materials data from all projects
• Database deployed for data input by Material Centers April 2010
• Public website will be launched first quarter of fiscal year 2011o Site will be searchable
by materials propertieso Data can be exported
in various formso New materials data can
be submitted for addition to public site
8
0
2
4
6
8
10
12
14
16
-200 -100 0 100 200 300 400
Obs
erve
d H
2C
apac
ity, w
eigh
t %
Temperature for observed H2 release (ºC)
LiBH4/CA
Ca(BH4)2
Mg(BH4)2
LiNH2/MgH2
MgH2
LiMn(BH4)3NaAlH4
Li3AlH6/LiNH2
solid AB (NH3BH3)
AlH3
liq. AB/cat.
1,6 naphthyridine
AB ionic liq.
IRMOF-177
PANI
M-doped CA
PCN-12
bridged cat./AX21
bridged cat./IRMOF-8
metal hydrides
sorbents
chemical hydrides
carbide-derived C
M-B-N-H
PANI
H2 sorption temperature (ºC)0-100-200
Mg(BH4)2(NH3)2
Mg(BH4)(AlH4)
Mg(BH4)2(NH3)2
Li3AlH6/Mg(NH2)2
Material capacity must exceed
system targets
LiBH4/MgH2
LiMgN
Li-AB
MOF-74
AB/cat.
C aerogel
B/C
MD C-foam
NaMn(BH4)4
Na2Zr(BH4)6
?
CH Regen. Required
2015
Ultimate
MD C-foam
PANI
Ti-MOF-16
Mg-Li-B-N-HCa(BH4)2/2LiBH4
AlB4H11
2009 Progress & Accomplishments
Status at 2009 AMR Review
9
0
2
4
6
8
10
12
14
16
-200 -100 0 100 200 300 400
Obs
erve
d H
2C
apac
ity, w
eigh
t %
Temperature for observed H2 release (ºC)
LiMgN
LiBH4/CA
Ca(BH4)2
Mg(BH4)2
LiNH2/MgH2
MgH2
NaAlH4
Li3AlH6/LiNH2
solid AB (NH3BH3)
1,6 naphthyridine
AB ionic liq.
IRMOF-177
PANI
PCN-12
metal hydrides
sorbents
chemical hydrides
carbide-derived C
M-B-N-H
PANI
H2 sorption temperature (ºC)
0-100-200
Mg(BH4)2(NH3)2
Mg(BH4)(AlH4)
Mg(BH4)2(NH3)2
Li3AlH6/Mg(NH2)2
Material capacity must exceed
system targets
LiBH4/MgH2
MOF-74
C aerogel
B/C
Open symbols denote new materials since 2009 AMR
NaMn(BH4)4
2015
AlB4H11
Ca(BH4)2/2LiBH4
Mg-Li-B-N-H
Na2Zr(BH4)6
LiMn(BH4)3
Mg(BH4)2(NH3)2
CsC24 CsC24
BC8
AC (AX-21)
MPK/PI-6PCN-6
MD C-foam
LiBH4/Mg2NiH4
bridged cat./IRMOF-8
Ti-MOF-16
Bridged cat/AX21 BC8C123BF8 AC(AX-21)M-doped CA
LiAB
KAB
DADB
AlH3AB/LiNH2
Liq AB:MeAB
AB/AT/PS soln
AB/Cat.
Li-AB
Ca(AB)2
Ti(AB)4
AB+AF(Me-Cell)AB/IL (20% bminCl)
LiMgN
LiBH4/CA
Ca(BH4)2
Mg(BH4)2
LiNH2/MgH2
MgH2
NaAlH4
Li3AlH6/LiNH2
solid AB (NH3BH3)
1,6 naphthyridine
AB ionic liq.
IRMOF-177
PANI
PCN-12
metal hydrides
sorbents
chemical hydrides
carbide-derived C
M-B-N-H
PANI
H2 sorption temperature (ºC)
0-100-200
Mg(BH4)2(NH3)2
Mg(BH4)(AlH4)
Mg(BH4)2(NH3)2
Li3AlH6/Mg(NH2)2
Material capacity must exceed
system targets
LiBH4/MgH2
MOF-74
C aerogel
B/C
Open symbols denote new materials since 2009 AMR
NaMn(BH4)4
2015
AlB4H11
Ca(BH4)2/2LiBH4
Mg-Li-B-N-H
Na2Zr(BH4)6
LiMn(BH4)3
Mg(BH4)2(NH3)2
CsC24 CsC24
BC8
AC (AX-21)
MPK/PI-6PCN-6
MD C-foam
LiBH4/Mg2NiH4
bridged cat./IRMOF-8
Ti-MOF-16
Bridged cat/AX21 BC8C123BF8 AC(AX-21)M-doped CA
LiAB
KAB
DADB
AlH3AB/LiNH2
Liq AB:MeAB
AB/AT/PS soln
AB/Cat.
Li-AB
Ca(AB)2
Ti(AB)4
AB+AF(Me-Cell)AB/IL (20% bminCl)
Ultimate
2010 Progress & Accomplishments
101010
2010 Progress: Engineering CoE
Modeling of Storage Systems
(SRNL)
Focus on model development and material evaluation
Acceptability EnvelopeThe “Acceptability Envelope” or “BlackBox Analysis” determines range of characteristics necessary for coupled media and system
to meet storage system performance targets
System Architect Analysis Applying Acceptability Envelope
Model to Various Materials
8.07.06.05.04.03.02.01.00.0
Wt%
.040
.035
.030
.025
.020
.015
.010
.005
.000
Suggests that Li-Mg-N materials
may be the most
promising metal
hydrides for further
consideration
Pure Material Graphite Enhanced Material
L(m
)
(SRNL)L(m) is the distance between heat transfer elements in meters
11
2010 Progress: Engineering CoESystems evaluated against complete set of performance targets
Adsorbent System Status (AX-21 Cryo-Adsorbent)
Chemical Hydride System (Solid Ammonia-Borane Bed)
Metal Hydrides (NaAlH4)
0%
100%Gravimetric Density
Volumetric Density
Minimum Operating Temperature
Maximum Operating Temperature
Min. Delivery Temperature
Max Delivery Temperature
Cycle Life (1/4 - full)
Cycle Life (90% confidence)
Min. Delivery Pressure (PEMFC)
Max. Delivery PressureOn Board EfficiencyFill Time (5Kg H2)
Minimum Full Flow Rate
Start Time to Full Flow (20oC)
Start Time to Full Flow (-20oC)
Transient Response
Fuel Purity
Permiation & Leakage
Toxicity
Safety
Loss of Useable H2
0%
100%Gravimetric Density
Volumetric Density
Minimum Operating Temperature
Maximum Operating Temperature
Min. Delivery Temperature
Max Delivery Temperature
Cycle Life (1/4 - full)
Cycle Life (90% confidence)
Min. Delivery Pressure (PEMFC)
Max. Delivery Pressure
On Board EfficiencyFill Time (5Kg H2)
Minimum Full Flow Rate
Start Time to Full Flow (20oC)
Start Time to Full Flow (-20oC)
Transient Response
Fuel Purity
Permiation & Leakage
Toxicity
Safety
Loss of Useable H2
12
2010 Progress: Materials
Hydride Destabilization
• Destabilization results in lower ∆H and T1 bar
LiBH4/Mg2NiH4 system• ΔH (= 15 kJ/mol-H2) and
ΔS (= 62 J/ K-mol-H2) are the lowest reported so far for a reversible system
(HRL)
AlH3 RegenerationStep 1: Five pathways identified to form AlH3 adducts from H2 and AlStep 2: Transamination demonstrated with high yields for DMEA and TMA.Step 3: TEA-AlH3 separated with ~70% recovered AlH3
ANL analysis of WTT efficiency suggests 55% possible with TMA
route using waste heat(BNL)
Progress being made in reversible metal hydride material discovery
Role of Additives on H2release from Mg(BH4)2
• Small amount of boron hydrides (15 – 58 amu) (<0.2wt%) is released
• Other transition metal halides were tested but were not as effective
• The catalysts have little or no effect on rehydrogenation
List what additives were used
AlH3 Generated Electrochemically• ElectroCatalytic Additive found to increase
steady-state current by 80%
• Dramatic increase in production rates.
(SRNL)
13
• Ti on clean Al surface critical for dissociating molecular hydrogen.
• Enables formation of mobile AlHx entities on the surface
Aluminum on Silicon with no Ti
Aluminum on Silicon with Ti
No Hydrogen exposure
Al
Ti Ti
VAl Hx
With Hydrogen exposure Role of Ti on the reaction
of H2 with Al
2010 Progress: MaterialsUnderstanding the role of additives in hydrogen uptake reactions
Impurities PNNL and LANL developed methods for quantification and strategies for mitigation of impurities released during hydrogen release from ammonia borane. Catalysts and additives reduce the release of borazine into the gas stream.
Chemical Hydrogen Storage Material
Coupling exothermic BHNH release with endothermic H-C-C-H in the same molecule is a successful approach
14
=“one-pot” regenQuantitative conversion by NMR
H2B
H2NBH2
H2N
BH2
H2N
BH2
NH2
BH2
H2N
AB + N2N2H4
NH3
• Method gives ammonia borane for multiple spent fuel forms.
• Improvements in process efficiency and capital cost should result from the lower mass throughput (relative to previous process)
AmmoniaBorane
HydrazineNH3 (liquid)
60 °C
Spent FuelN
B N
B
NB
B
HN
B NH
B
NHHB
HN
HB NH
B
NH
NHB
N
HB N
BH
N2H4excess liq. NH3
AB + N2
Spent Fuel60 C
2010 Progress: Materials
Regeneration of Spent Fuels
G at 298K(kcal/mol)
BH2
HN
BHNH vs.
BH2
HN
BHN
t-Bu t-BuH
Material (1) more readily available model of (1)
= –2.3 G at 298K(kcal/mol) = –0.4
NB
H
t-BuNB
H
t-BuNB
H
t-BuNB
H
t-BuNB
H
t-Bu
1
Rehydrogenates under mild conditions
New Materials from University of Oregon:
• Prepared models of compound 1 at stages of dehydrogenation
• Demonstrated simple regeneration chemistry
Chemical Hydrogen Storage Material
2010 Progress: SorbentsAccomplishments: Cryosorbents
Stabilization of MOFs with High Surface Areas by the Incorporation of Mesocavities
with Microwindows
77K
PCN-61 PCN-66 PCN-68
PCN-68: 6033 m2/g Langmuir (5109 m2/g BET) and ~ 7.2 wt% excess H2 capacity TAMU; Data by GM
• Achieved H2 uptake of 5.1w% at 77K and 0.6w% at RT
• Observed H2 isosteric heat of adsorption up to ~10 kJ/mol over selected POPs
• Polyporphyrin can serve as platform for exchanging transition metals for H-M interaction
ANL/Univ. of ChicagoNanostructured polyporphyrin based organic polymer
0.0 2.0x1017 4.0x1017 6.0x1017 8.0x1017 1.0x1018
6
7
8
Heat
of A
dsor
ptio
n (k
J/mol
)
Hydrogen Loading (m-2)
Derived from 195 K and 298 K isotherms
∆Hads measurement
FeTTPP
PTTPP
2010 Progress: SorbentsAccomplishments: Towards Room Temperature & Moderate Pressure Conditions
NREL
NIST and Penn State
Boron substituted carbons• Quantitative B-H interactions observed for the first
time• Neutron data shows, for the first time, a large rotational
splitting indicative of enhanced H2 interactions in a substituted carbon
• DRIFTS observes reversible H interaction in B-C materials• Experimental results confirm calculations that B-C
increases ΔH values 16INS: H2 rotational spectra
Bulk H2 rotation
Weak Chemisorption MaterialsPt/ Carbon from Pyrolyzed Sucrose on Silica Sphere Templates
• Excellent Kinetics: < 5 min to saturation• Adsorption of hydrogen still increasing at 150 bar • Minimal irreversibility. Multiple cycles with no loss
of sorption capacity or water formation.• Demonstrates unique features of pyrolized sucrose
that is used for “bridging” to MOFs• Unexpected capacity on “small” surface area, 600
m2/g (Pt content 10wt%)• Possibility of “hidden” pore structure needs to be
determined
RT
1717
2010 Status: Compressed GasThe carbon fiber composite layer accounts for about 75% and 80% of the
350-bar and 700-bar base case system costs, respectively.
TIAX
Based on manufacturing volumes of 500,000 units per annum., weight and volume under review
The Storage Program is currently funding ORNL to develop lower cost precursors (i.e., melt spinnable PAN and polyolefins) and reduced production costs for high-strength carbon fibers.ORNL early runs produced melt-spun
PAN filaments of moderate qualityPrecursor and Conversion Estimated CF Cost
$/lb CFBaseline – Wet spun PAN precursor conventionally converted
$11.43
Melt spun PAN, advanced ORNL conversion $ 6.11
18 g/L 26 g/L
4.8 wt%5.85 wt%
18
2010 Progress: Analysis
ANL/TIAX analyses indicate that scaling vessel size to store 5.6 kg H2 for a passenger vehicle reduces capacities to 5.5 wt% H2 at 42 g H2/L at lower cost than a 700-bar Compressed gas tank.
The 3rd generation cryogenic pressure vessel prototypesaves 25 kg and 70 L compared to the previous 2nd generation prototype for storing 10.7 kg H2 at 7.1 wt% H2 and 44.5 kg H2/L (LLNL)
Cryogenic pressure vessels offer potential to exceed 2015 H2 storage goals
Hydrogen RI Port
Regular
Valves
Other BOP
Linear and Fittings
Carbon Fiber Layer
MLVI
Outer Shell
Balance of Tank
5.8 kg Base Case Weight = 102 kg5.5 wt% based on 5.6 kg usage LH2
HydrogenFill PortRegulator
Valves
Other BOP
Liner and Fittings
Carbon Fiber Layer
MLVIOuter Shell Balance of
Tank
5.8 kg Base Case Volume = 131 L43 g H2/L based on 5.6 kg usable LH2
Hydrogen Assembly and
Inspection
Fill Port
Regular
Valves
Other BOPLinear and Fittings
Carbon Fiber Layer
MLVIOuter Shell
5.8 kg Base Case Factory Cost1 = $2,200$12/kWh based on 5.6 kg useable LH2
3rd generation cryogenic pressure vessel prototype
2nd generation cryogenic pressure vessel prototype
2010 Progress: AnalysisMetal Organic Frameworks Adiabatic Liquid H2 Refueling Analysis
70
80
90
100
110
Opt
imum
Sto
rage
T (K
)
0
5
10
15
20
Opt
imum
DT
(K)
DT
T
10
20
30
40
0 50 100 150 200 250 300 350Storage Pressure (atm)
Sys.
Vol
. Cap
. (kg
/m3 )
4.0
4.5
5.0
5.5
Sys.
Gra
v. C
ap. (
wt%
)
MOF-177Minimum P = 4 atm
Gravimetric
Volumetric
System gravimetric capacity peaks at ~150 atm but the volumetric capacity increases slowly with storage pressure
Refueling: 7.1 MJ evaporative cooling load– 62% for ∆H, 38% for
sensible cooling and PV work
Discharge options– Constant Q (1.2 kJ/g of
H2 discharged), 1.9 kW – Variable Q, heat supplied
only if tank P < 4 atm, 6.3-kW peak Q
Spent Fuel
Recycle
GLS
AB/IL Fuel
Spent Fuel
LTC: Low Temperature CoolantHTC: High Temperature CoolantPLV: Pressure Letdown ValveGLS: Gas-Liquid Separator
Startup Heater
To LT Radiator Dehydrogenation
Reactor
To HT Radiator
H2
H2
H2 Buffer Tank
GateValve
LTC
HTC
PLV
• Substantial spent fuel recycle to manage exothermic release
• Heat rejection and startup/shutdown are key challenges
Onboard release system: Preliminary ANL analysis of ionic liquid/ammonia borane liquid mixtures developed in Sneddon’s group at U. Penn with material capacities up to 11 wt. %, and fast release rates above 85 C identified:
Borane Liquid Mixture Analysis
19
Performance & Cost Metric
MOF-177 Units
System Gravimetric Capacity 4.1 Wt%
System Volumetric Capacity 34.1 Kg-H2/m3
Storage System Cost 18 $/kWh
Fuel Cost 4.6 $/gge
Cycle Life (1/4 full tank) 5500 Cycles
Min Delivery Pressure 4 atm
System Fill Rate 1.5 – 2 Kg-H2/min
Min Dormancy (full tank) 2.8 W – d
H2 Loss Rate (Max) 0.9 g/h/kg-H2
WTT Efficiency 41.1 %
GHG Emissions (CO2 eq) 19.7 kg/kg-H2
Ownership Cost 0.15 $/mile
20
Congratulations to the3 Presidential Awardees:
• Professor Susan Kauzlarich – UC Davis, a 2009 recipient of the Presidential Award for Excellence in Science, Mathematics and Engineering Mentoring—and a partner of the Chemical Hydrogen Storage Center of Excellence
• Dr. Jason Graetz – Brookhaven National Laboratory, a 2009 recipient of the Presidential Early Career Award for Scientists and Engineers—and a partner of the Metal Hydride Center of Excellence
• Dr. Craig Brown – NIST, a 2009 recipient of the Presidential Early Career Award for Scientists and Engineers—and a Partner of the Hydrogen Sorption Center of Excellence
2009 Presidential Awardees in Program
21
Summary
Major Upcoming Milestones
Physical Storage • Initially tasks were not planned beyond FY2010 because physical storage was not seen as a pathway towards meeting the
ultimate targets.o Physical Storage will be used for early automotive market penetration as well as other early markets;o Additional tasks will be planned and added for out years, especially focusing on cost reduction.
Material-based Storage• Three Material-based Centers of Excellence established in FY2004 and are being completed in FY2010;• Hydrogen Storage Engineering Center of Excellence established in FY2009 as a 5-year effort;• New materials R&D efforts are needed to further develop storage materials and to support the engineering efforts.
FY 2010 FY 2011 FY 2012
O O JJJ A AAJ JJ O2010 2011 2012
4Q 2010: Output to Tech Val—report on advanced compressed/cryogenic tank technologies
4Q 2013: Down select on-board reversible storage materials with potential to meet 2015 targets
4Q 2013: Down-select hydrogen storage approaches with potential to meet 2015 targets
3Q 2011 EoC: Provide a system model for eachmaterial sub-class (metal hydride, adsorption, chemical hydride)
2Q 2012: ECoE: Provide at least one full scale system design concept
4Q 2010: Final Report due for Material Centers of Excellence
1Q2 011: Hydrogen Storage Materials Database Released to Public
Potential FOA Release
22
Session Instructions
• This is a review, not a conference.
• Presentations will begin precisely at the scheduled times.
• Talks will be 20 minutes and Q&A 10 minutes.
• Reviewers have priority for questions over the general audience.
• Reviewers should be seated in front of the room for convenient access by the microphone attendants during the Q&A.
• Please mute all cell phones, BlackBerries, etc.
23
Reviewer Reminders
• Deadline for final review form submittal is June 18th.
• ORISE personnel are available on-site for assistance. A reviewer lab is set-up in room 8216 and will be open Tuesday –Thursday from 7:30 AM to 6:00 PM and Friday 7:30 AM to 3:00 PM.
• Reviewer feedback session – Thursday, at 6:15pm (after last Hydrogen Storage session), in this room.
24
For More Information
Storage Team Contacts
Ned T. StetsonActing Hydrogen Team Leader
Metal Hydrides
Grace OrdazChemical Hydrogen Storage Materials
Carole ReadHydrogen Sorbents
Monterey GardinerPhysical Storage, Engineering
Technical Support: Robert C. Bowman, Jr. (ORNL)
Anita Vanek (BCS)Kristian Whitehouse (Navarro)
Golden Field Office Project Officers:Jesse AdamsJames AlkirePaul Bakke
Katie Randolph
