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

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

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

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

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

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

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

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

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

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 14687-2 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

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

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

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

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

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

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

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

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

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

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

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

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)

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…

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

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

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

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)

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

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

Does ISO 14687-2 need to be revised? The future… Revision of ISO 14687-2 Does ISO 14687-2 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

Hydrogen purity in the future The next steps for hydrogen purity Revised ISO 14687-2 standard Further development of traceable offline methods Hydrogen impurity enrichment device Develop the online purity analyser HIED

Quality assurance of hydrogen for fuel cell vehicles – removing the roadblock Arul Murugan and Andrew S. Brown THANK YOU Please email: arul.murugan@npl.co.uk