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Michael A. MillerStaff Scientist
Richard PageInstitute Scientist
Southwest Research InstituteSan Antonio, TX
DOE Annual Merit ReviewWashington DCMay 18, 2006
Michael A. MillerStaff Scientist
Richard PageInstitute Scientist
Southwest Research InstituteSan Antonio, TX
DOE Annual Merit ReviewWashington DCMay 18, 2006
National Testing Laboratory for Solid-State Hydrogen Storage Technologies
National Testing Laboratory for Solid-State Hydrogen Storage Technologies
This presentation does not contain any proprietary or confidential information Project ID #: STP 34
2
OverviewOverview
• Standardization of Methods• “Gold Standard” Measurements• Verification of Material Performance
Understanding of Physisorption & ChemisorptionProcessesReproducibility of Performance
• Verification of System PerformanceReproducibility of PerformanceSystem Life-Cycle Assessment
• Codes & Standards
• Program Start: March 2002• Program End: September 2006• 99% Complete
TimelineTimeline BarriersBarriers
• Total Program Funding:DOE Share: $2.4MSwRI Share: $0.62M
• Funding Received in FY05: $415k• Funding Received in FY06: $50K
• National Hydrogen Association (Standards)
• Ovonic Hydrogen Systems (Full-scale storage systems)
• NESSHY (EC-JRC)• NREL• INER (Taiwan)
BudgetBudget Partners / CollaborationsPartners / Collaborations
3
ObjectivesObjectivesOverallOverall• Construct and operate a national-level research and core reference
laboratory aimed at assessing and validating the performance of emergent solid-state hydrogen storage materials and full-scale systems
• Establish “gold standard” measurement techniques for hydrogen sorption and related performance metrics
CurrentCurrent• Qualify laboratory based on outcome of double-blind Round-Robin testing• Assist NREL in independent analysis of SWNT materials• Improve and refine measurement techniques to accommodate most any
structure of matter, thermal condition, and sample quantity• Complete testing laboratory for full-scale hydrogen storage systems
Capacity?Capacity?
Kinetics?Kinetics?
Thermodynamics?Thermodynamics?
Cycle life?Cycle life?
4
Equilibrium Pressure (bar)
0 10 20 30 40 50 60 70 80 90
Hyd
roge
n Ex
cess
Ads
orpt
ion
(wt.%
)
0.0
0.1
0.2
0.3
0.4
0.5
0.6Volumetric - CNI3-PGravimetric - CNI3-PVolumetric - TR-AC1Gravimetric - NREL CHKWGravimetric - UTenn CarbosieveGravimetric - TR-AC1
Isotherm: 25°C
ApproachApproach
Refine Analytical Methods1. Low-temperature measurements2. Thermal gradient correction3. Small sample mass4. Sample vessel optimization
Completion of Small-Scale Lab• System Shakedown• Draft SOPs
Lab Facility Design & Instrumentation Selection
05/01/200501/16/2004
09/05/2005
Qualification of Small-Scale Lab:• Internal controls• Round-Robin Testing
CarbonMetal hydride
05/06/2005
Completed Analysis of R-RCarbon Samples & Submitted Results
08/31/2005
Completed Independent Validationof NREL Measurements:1. Two SWNT Samples2. Three Catalyzed SWNT Samples
03/16/2006
Continuous
Revise SOPs(Small-Scale)
Completion of Full-Scale Lab
Agilent C hem Stat ion
Catalyzed SWNTs
Time (sec)
0 200 400 600 800 1000 1200 1400 1600 1800
Des
orpt
ion
Rat
e ( μ
mol
/sec
)
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Tem
pera
ture
(C)
-200
0
200
400
600
800
1000
m/z = 2Thermal Ramp
300 400 500 600 700 800
5
Technical AccomplishmentsTechnical AccomplishmentsCompletion & Validation of Laser Thermal Completion & Validation of Laser Thermal DesorptionDesorption Mass SpectrometerMass Spectrometer
Ytterbium Laser & Optical BenchYtterbium Laser & Optical Bench
• Quantitative and highly sensitive• Suitable for desorption of small
sample quantities (< 50 mg)• Resolves relative energies of
different physisorbed or chemisorbed hydrogen binding sites
6
Technical AccomplishmentsTechnical Accomplishments
• Full-pressure PCT and sorption isotherms
• Extended vacuum capability using logic control
• Real-time mass spectrometry• Sample vessel optimized for
better sample compactness and consistent thermal diffusivity
Completion & Validation of HighCompletion & Validation of High--Pressure Volumetric AnalyzerPressure Volumetric Analyzer
Capillary MS InterfaceCapillary MS Interface
Vacuum Logic ControlVacuum Logic Control
BacksideBackside
ManualV0
Regulator
V10 V9
V11 V8
V7
Supply
V6
V5V4
V3
CalibratedLarge Reservoir
CalibratedSmall Reservoir
V2
V1MS Interface
Vent
Vacuum
Hydrogen
Helium
Low PressureTransducer (0-5 bar)
High PressureTransducer
Check Valve
Sample Vessel
Sample Insert
TC Well
TC
7
Technical AccomplishmentsTechnical Accomplishments
• Full-pressure PCT and sorption isotherms
• Sample vessel optimized for more accurate buoyancy correction
• Real-time mass spectrometry• Cryogenic cooling attachment
under development
Completion & Validation of HighCompletion & Validation of High--Pressure Gravimetric AnalyzerPressure Gravimetric Analyzer
Capillary MS InterfaceCapillary MS Interface
Furnace / CoolerFurnace / Cooler
QMSQMS
MicrobalanceMicrobalance
8
Technical AccomplishmentsTechnical Accomplishments
• Refined technique and apparatus for low-temperature volumetric measurements by examining the relationship between critical point effects and free volume
• Sample compaction crucial in minimizing susceptibility of system to density fluctuations and measurement inaccuracies
• Determined an optimum vessel design• Improved thermal diffusivity and stability
Understanding Critical Point Effects and Free Volumes in HUnderstanding Critical Point Effects and Free Volumes in H22 SorptionSorptionSilicon Temperature Correction at 77 K
Concentration (wt.% H)
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Equi
libriu
m P
ress
ure
(bar
)
0
10
20
30
40
50
60
70
80
No CorrectionCf = 0.235Cf = 0.24
Pc
Tc = 32.19 K
Supercritical Region
Density Fluctuations of Gasin Free Volume
Bulk Bulk
RCP Model RCP Model WireWire--FrameFramePolyhedraPolyhedra
Interstitial VolumeInterstitial Volume
SurfaceSurfaceLayer Layer
Packing Density ConsiderationsPacking Density Considerations
Optimized Sample Vessel Optimized Sample Vessel
9
Technical AccomplishmentsTechnical Accomplishments
• Room temperature results consistent with those of outside participant labs (n=6)• Gained detailed understanding of important factors affecting the accuracy of low-
temperature physisorption measurements• Low temperature isotherm results also consistent with those of outside participant
labs after refining measurement technique and apparatus
Round Robin Sample: Carbon Sample 2
Equilibrium Pressure (bar)
-10 0 10 20 30 40 50 60 70 80
Exce
ss C
once
ntra
tion
(wt.%
H)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
298 K77 K
Round Robin Sample: Carbon Sample 1
Equilibrium Pressure (bar)
-10 0 10 20 30 40 50 60 70 80
Exce
ss C
once
ntra
tion
(wt.%
H)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
77 K298 KGravimetric Analysis, 298 K
RoundRound--Robin Results: Volumetric & Gravimetric MeasurementsRobin Results: Volumetric & Gravimetric Measurements
10
Equilibrium Pressure (bar)
0 10 20 30 40 50 60 70 80 90
Hyd
roge
n Ex
cess
Ads
orpt
ion
(wt.%
)
0.0
0.1
0.2
0.3
0.4
0.5
0.6Volumetric - R-R Carbon Sample 1Gravimetric - R-R Carbon Sample 1Volumetric - R-R Carbon Sample 2Gravimetric - R-R Carbon Sample 2Gravimetric - SWNTGravimetric - Porous Carbon
Isotherm: 298 K
Technical AccomplishmentsTechnical Accomplishments
• Demonstrated excellent complementarity between volumetric and gravimetric measurements
• Hydrogen physisorption on various carbon materials (non-catalyzed) is limited to < 0.5 wt.% at room temperature
Measurements of Various Carbon Materials at Room TemperatureMeasurements of Various Carbon Materials at Room Temperature
11
Technical AccomplishmentsTechnical Accomplishments
• Demonstrated capability of measuring very small sample quantities (< 10 mg)• SwRI measured hydrogen capacity consistent with previously published data†
Evaluation of Catalyzed Evaluation of Catalyzed SWNTsSWNTs from NREL: Validation of Hfrom NREL: Validation of H22 Capacity Capacity by Thermal by Thermal DesorptionDesorption Mass SpectrometryMass Spectrometry
Catalyzed SWNTs
Time (sec)
0 200 400 600 800 1000 1200 1400 1600 1800
Rel
ativ
e Si
gnal
Inte
nsity
10-7
10-6
10-5
10-4
10-3
10-2
10-1
Tem
pera
ture
(C)
-200
0
200
400
600
800
m/z = 2m/z = 14m/z = 18m/z = 28m/z = 32m/z = 44Thermal Ramp
Catalyzed SWNTs
Time (sec)
0 200 400 600 800 1000 1200 1400 1600 1800
Des
orpt
ion
Rat
e ( μ
mol
/sec
)
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Tem
pera
ture
(C)
-200
0
200
400
600
800
1000
m/z = 2Thermal Ramp
300 400 500 600 700 800
Measured Measured DesorptionDesorption: 2.78 wt.%: 2.78 wt.%
† A.C. Dillon, K.M. Jones, T.A.Bekkedahl, C.H. Kiang, D.S. Bethune, & M.J. Heben, Nature (386) 377, 1997.
MultiMulti--Ion Monitoring of Desorbed SpeciesIon Monitoring of Desorbed Species
12
Technical AccomplishmentsTechnical AccomplishmentsCompletion of FullCompletion of Full--Scale Laboratory FacilityScale Laboratory Facility
Characterization of the performance of full-size storage systems to include:• Sorption/desorption performance• Refueling time• Resistance to exogenous contaminates• Specific energy contained• Impact, vibration and fire resistance
13
Future WorkFuture Work
Program / Sample Backlog1. US DOE2. US Commercial3. NESSHY (EC)4. INER (Taiwan)
Full-Scale Lab Facility
Small-Scale Lab Facility Complete Round-Robin Testingof Metal Hydride Samples
Facility Benchmarking
07/01/2006
Commence 07/01/2006
Fiber-Wrapped
Vessel
Aluminum Tubular Vessel
H2Capacity 1.7 kg 0.7 kg
Diameter 11 in. 6 in.
Length 31.3 in. 60 in.
Weight 127 kg 81 kg
OvonicOvonic Hydrogen SystemsHydrogen Systems
14
SummarySummaryRelevance: Provide DOE with facilities to independently assess the
performance of solid state storage materials
Approach: Construct and operate a national-level research and core reference laboratory aimed at assessing and validating the performance of emergent solid-state hydrogen storage materials and full-scale systems
Technical Accomplishments: Completed laboratory containing gravimetric, volumetric and TPD instrumentation; room temperature and low temperature results on round robin carbon samples consistent with those of outside participant labs
Collaborations: Active collaborations with NESSHY (EC-JRC), NREL and INER (Taiwan)
Future Research: Improve and refine measurement techniques to accommodate most any structure of matter, thermal condition, andsample quantity; complete testing laboratory for full-scale hydrogen storage systems
15
Response to Reviewer’s CommentsResponse to Reviewer’s Comments
• Sample shipping restrictions may be a significant impediment
• Began to address shipping issues with presentation at workshop• Shipping and receipt protocols have been developed
• Need more effort on characterizing smaller samples• Current TGA and TPD systems are available for 10-100mg
samples• Future plans to modify volumetric system for 10-100mg samples
• Burst chamber for tanks too small for automotive scaled tanks
• Chambers are adequate for current tanks up to at least 2 kg capacity
• Modifications are possible for larger or unusual shaped tanks
16
Publications & PresentationsPublications & Presentations
1. M.A. Miller and R.A. Page, National Testing Laboratory for Solid-State Hydrogen Storage Technologies, NHA National Hydrogen Conference, Washington, DC, March 29 – April 1, 2005
2. M.A. Miller and N. Sridhar, Measurement and Prediction of Material Performance Subject to Hydrogen Exposure, Hydrogen Gas Embrittlement Workshop, ASTM T.G. 01.06.08, ASTM Meeting, Reno, NV, May 17, 2005
3. M.A. Miller, Development and Application of Standard Methods forQuantifying Hydrogen Sorption in Nanostructured Materials, 2005 Taiwan Symposium on Hydrogen Storage in CNMs, Institute of Nuclear Energy Research (INER), Taipai, Taiwan, Oct. 18-19, 2005
17
Critical Assumptions & IssuesCritical Assumptions & Issues
Assumption: Sufficient quantities of research grade samples willrequire independent verification
• Round-robin testing program designed to optimize acceptance of facility
• Rate of development of promising materials that require independent verification is uncertain
Assumption: Progress in the development of full-scale storage systems will be sufficient to adequately utilize the testing facility
• Independent verification of promising results on new materials should speed system development
• Rate of system development is uncertain
Assumption: Facility will have the instrumentation and protocolsnecessary to evaluate as yet undeveloped materials
• Facility team needs to keep abreast of current developments within community
• Facility team and DOE need to remain flexible in defining the instruments and protocols in the facility
