1. Quality assurance of hydrogen for fuel cell vehicles – removing the roadblock
Arul Murugan and Andrew S. Brown

2. Overview of todays presentation
Hydrogen energy & recent progress
NPL hydrogen purity analysis
The future…

3. H2 + ½O2  H2O Why hydrogen energy? Hydrogen has a high energy density
Hydrogen energy & recent progress
Why hydrogen energy?
Hydrogen has a high energy density
Can be generated from water using renewable energy
H2 + ½O2  H2O
Used to power fuel cell vehicles
No carbon-containing products

4. H2 + ½O2  H2O Why hydrogen energy? Hydrogen has a high energy density
Hydrogen energy & recent progress
Why hydrogen energy?
Hydrogen has a high energy density
Can be generated from water using renewable energy
142 MJ per kg of H2!
H2 + ½O2  H2O
Used to power fuel cell vehicles
No carbon-containing products

5. H2 + ½O2  H2O Why hydrogen energy? Hydrogen has a high energy density
Hydrogen energy & recent progress
Why hydrogen energy?
Hydrogen has a high energy density
Can be generated from water using renewable energy
Water
Wind power
Electrolysis
H2 + ½O2  H2O
Used to power fuel cell vehicles
No carbon-containing products

6. H2 + ½O2  H2O Why hydrogen energy? Hydrogen has a high energy density
Hydrogen energy & recent progress
Why hydrogen energy?
Hydrogen has a high energy density
Can be generated from water using renewable energy
Water
Wind power
Electrolysis
H2 + ½O2  H2O
Used to power fuel cell vehicles
No carbon-containing products

7. H2 + ½O2  H2O Why hydrogen energy? Hydrogen has a high energy density
Hydrogen energy & recent progress
Why hydrogen energy?
Hydrogen has a high energy density
Can be generated from water using renewable energy
Water
Wind power
Electrolysis
H2 + ½O2  H2O
Used to power fuel cell vehicles
No carbon-containing products
High efficiency

8. UK Hydrogen Economy in 2030 Hydrogen energy & recent progress
A report by UK H2Mobility (2013)
1.6 million fuel cell vehicles on the road in the UK
1,100 hydrogen refuelling stations in operation
254,000 tonnes of hydrogen produced a year

9. Hydrogen energy & recent progress
Fuel cell degradation
Usually platinum – can degrade in the presence of impurities
(such as hydrogen sulphide or carbon monoxide)

10. Amount fraction limit (ppm)
Hydrogen energy & recent progress
Hydrogen purity requirements
The proposed EC Directive on the deployment of an alternative fuels infrastructure sets out that:
“Hydrogen refuelling points shall comply with the relevant EN standard, to be adopted by 2014, and, pending publication of this standard, with the technical specifications included in the ISO standard.”
Impurity
Amount fraction limit (ppm)
Water 5
Total hydrocarbons 2
Oxygen
Helium
300
Nitrogen
100
Argon
Carbon dioxide
Carbon monoxide
0.2
Total sulphur compounds
0.004
Formaldehyde
0.01
Formic acid
Ammonia
0.1
Total halogenated compounds
0.05
Fuel storage
Efficiency
Fuel cell degradation

11. Overview of todays presentation
Hydrogen energy & recent progress
NPL hydrogen purity analysis
The future…

12. NPL’s analysers NPL hydrogen purity analysis Helium Water Hydrocarbons
Gas chromatography with thermal conductivity detector
Quartz crystal microbalance
Water
Helium
Hydrocarbons
Formaldehyde
Carbon dioxide
Under development…
Gas chromatography with mass spectrometer detector
(or cavity ringdown spectroscopy)
Formic acid
Methane
Gas chromatography with methaniser and flame ionisation detector (backflush capability for hydrocarbons)
Ammonia
Carbon monoxide
Sulphur Compounds
Oxygen
Nitrogen
Argon
Gas chromatography with pulsed discharge helium ionisation detector
Gas chromatography with sulphur chemiluminescence detector

13. NPL hydrogen purity analysis
Island Hydrogen (TSB)
“Powering the island using only renewable energy”
NPL
Isle of Wight

14. NPL hydrogen purity analysis
Island Hydrogen (TSB)
“Powering the island using only renewable energy”
NPL
Wind power
Wind power
Isle of Wight
Power to homes

15. NPL hydrogen purity analysis
Island Hydrogen (TSB)
“Powering the island using only renewable energy”
Water
NPL
Surplus energy
Electrolysis
Excess wind
Wind power
Hydrogen storage
Isle of Wight
Power to homes

16. NPL hydrogen purity analysis
Island Hydrogen (TSB)
“Powering the island using only renewable energy”
Water
NPL
Electrolysis
No wind
Wind power
Hydrogen storage
Isle of Wight
Power to homes

17. NPL hydrogen purity analysis
Island Hydrogen (TSB)
“Powering the island using only renewable energy”
Water
NPL
Electrolysis
Fuel cell vehicles
Wind power
Hydrogen storage
Isle of Wight
Power to homes

18. Island Hydrogen (TSB) NPL Isle of Wight NPL hydrogen purity analysis
Wind power
Electrolysis
Water
Power to homes
Hydrogen storage
Fuel cell vehicles
Isle of Wight
NPL
“Powering the island using only renewable energy”
Feedback of purity analysis to refuelling station
Sampling
Transport
Analysis

19. NPL hydrogen purity analysis
Unlocking the hydrogen energy
market (TSB)
“Develop an online hydrogen purity analyser using cascade laser based systems”
Method validation using traceable offline methods
Hydrogen refuelling station
Online analysis
Sampling
Transport
Offline analysis

20. H2FC: Hydrogen to fuel cells
NPL hydrogen purity analysis
H2FC: Hydrogen to fuel cells
“Reduce costs for full hydrogen purity analysis – by reducing number of analysers”
Helium
Water
Hydrocarbons
Formaldehyde
Carbon dioxide
Formic acid
Methane
Ammonia
Carbon monoxide
Sulphur Compounds
Oxygen
Limit of detection of GC-MS is too high to measure all impurities in one method
Nitrogen
Argon
Halogenated compounds
Gas chromatography with mass spectrometer
Impurity enrichment

21. H2FC: Hydrogen to fuel cells
NPL hydrogen purity analysis
H2FC: Hydrogen to fuel cells
Hydrogen
Impurity
Hydrogen sample
Measure krypton
Combine
Krypton
(Tracer)
Krypton
Enrichment
factor
Enrichment
factor
Hydrogen removal
(through palladium based membrane)
Measure krypton
Krypton in air is 1 ppm
Measure impurities using GC-MS
Hydrogen Impurity Enrichment Device (HIED) NPL’s tracer enrichment method

22. NPL hydrogen purity analysis
H2FC: Hydrogen to fuel cells
Paper published in RSC’s Analytical Methods journal
Selected as a HOT article by RSC
To be included in a special issue of the journal: ‘Emerging analytical methods for global energy and climate issues’
Advancing the analysis of impurities in hydrogen by use of a novel tracer enrichment method
– A. Murugan & A. S. Brown (2014)

23. H2FC: Hydrogen to fuel cells
NPL hydrogen purity analysis
H2FC: Hydrogen to fuel cells
Required membrane improvements (future work)
Avoid adsorption of impurities
To withstand high pressures
To withstand evacuation
Improved membrane lifetime
One of many conclusions:
Device works well, but further work required with regards to the improvement of palladium-based membranes…

24. NPL Innovation Research & Development Project
NPL hydrogen purity analysis
NPL Innovation Research & Development Project
“Develop a suite of characterisation tools to help improve palladium-based membranes”
Palladium-based membranes
Surface analysis techniques
Gas testing

25. Contaminated/damaged membranes
NPL hydrogen purity analysis
H2S and CO adsorption
SAES membranes
Testing chamber
NPL gas testing
Helium permeation tests
Evacuation rig
Evacuation testing
New membranes
Feedback of results
Contaminated/damaged membranes
Pressure testing
Pressure rig
SAES testing
Before
After
NPL characterisation
Microscopy
FIB-SEM
XPS
2D profiling
Roughness
Micro crack identification
3D layer profiling
Stress/
damage
Impurities on surface
Adsorbed layer thickness
Amount of adsorption

26. Overview of todays presentation
Hydrogen energy & recent progress
NPL hydrogen purity analysis
The future…

27. Fuel cell vehicles – 2015 The future… Hyundai ix35
Typical technical specifications for fuel cell vehicles to be available in 2015
Nissan X-Trail FCV SUV
Toyota FCV concept
UK H2 Mobility report (2013)

28. UK refuelling stations – 2015-2030
The future…
UK refuelling stations –
UK H2 Mobility report (2013)

29. Hydrogen purity laboratory
The future…
Hydrogen purity in the future?
HIED
Offline analysis
Hydrogen purity laboratory
Sampling
Transport
Hydrogen refuelling station
Online analyser
Providing traceable measurements and primary reference gas standards
Online analysis

30. Does ISO 14687-2 need to be revised?
The future…
Revision of ISO
Does ISO need to be revised?
only for hydride
storage
no one can measure
can this be increased?
specific to certain hydrogen production methods
Results from discussion at EC

31. Hydrogen purity in the future
The next steps for hydrogen purity
Revised ISO standard
Further development of traceable offline methods
Hydrogen impurity enrichment device
Develop the online purity analyser
HIED

32. Quality assurance of hydrogen for fuel cell vehicles – removing the roadblock Arul Murugan and Andrew S. Brown
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