Hydrogen Purity Analysis for Fuel Cell Vehicles

M. Downey, A. Brown and G. Vargha

National Physical Laboratory, Hampton Road, Teddington, Middlesex, TW11 0LW, UK michael.downey@npl.co.uk

The Driver
There is a pressing need to move away from the conventional fossil fuels used as vehicle fuels today due to their damaging environmental effects and dwindling resources. One solution is the use of hydrogen as a fuel as this would significantly reduce harmful emissions from vehicles as well as being potentially produced by renewable energy sources.
Species
Water Total hydrocarbons Oxygen Helium Nitrogen/Argon Carbon Dioxide Carbon Monoxide Total sulphur compounds Formaldehyde Formic acid Ammonia Total halogenated compounds Maximum particulates concentration

Maximum Concentration (mol/mol) (ppm)

5 2 5 300 100 2 0.2 0.004 0.01 0.2 0.1 0.05 1mg/kg

The Measurement Need

Impurities in hydrogen have a severe affect on the performance of fuel cells. For example at several hundred ppb carbon monoxide will poison the expensive platinum catalyst. It is therefore crucial to be able to detect any impurities before the fuel is used. An international standard ISO/DIS 14687-2a is being developed to highlight all of the impurities that need to be identified and at what level, these are illustrated on the left.

Analytical Challenges
Most of the impurities in the table are challenging in several different ways: some will be affected by air contamination (e.g. oxygen at 5ppm), others are at an extremely low level (e.g. 4ppb total sulphur species) and some species are not stable (e.g. formaldehyde). Preparation of stable gaseous reference materials for a number of these species is highly challenging.

Method Developments at NPL

A suite of methods have been developed to analyse impurities in hydrogen at or below the specification in ISO/DIS 14687-2. Two highlights are:
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1) Total Sulphur Compounds at 4ppb by GC-SCD Usually only achievable by pre-concentration. The challenge here is two-fold, firstly to be able to measure all sulphur species together, and secondly to achieve an extremely low LoD. NPL designed passivated cylinders and a bespoke sampling system to prevent any adsorption to surfaces were used. For the analysis, a column with very low retention was used to ensure that five different sulphur species would all elute as a single peak. The result was a calculated LoD of 1ppb. 2) O2, N2, CH4, and CO by GC-PDHID A novel pulsed discharge helium ionisation detection gas chromatography (GC-PDHID) method has been developed at NPL to measure very low levels of permanent gases including oxygen, nitrogen, methane and carbon monoxide. The method shows outstanding separation of the target impurities, LoDs for these species were calculated to be below 100ppb.

Conclusions
The target LoDs have been achieved for all species of key industrial importance (see chart). The new suite of methods has been tested on hydrogen samples produced by ITM Powers novel electrolytic hydrogen production facility. The results greatly pleased our collaborators and we look forward to working with them again in the near future.

Future Work
The next challenges are: Measurement of the remaining few species below the limits specified in ISO/DIS 14687-2. Development of a single method to analyse as many of the potential impurities as possible. GC-MS is the most promising technique to be able to do this. Development of a selective membrane system that can enrich the impurities within the hydrogen. Investigation into the effects of sampling hydrogen from 700bar sources on the levels of impurities.
a

Hydrogen fuel - Product Specification - Part 2: Proton exchange membrane (PEM) fuel cell applications for road vehicles

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