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Rechargeable PEM fuel cell with hydrogen storage polymer

Energy-converting devices such as fuel cells are among the most efficient and clean alternative energy-producing sources. They have the potential to replace fossil-fuel-based power generators. More specifically, proton exchange membrane fuel cells (PEMFCs) are promising energy conversion devices for residential, transportation and portable applications owing to their high power density and efficiency at low operating temperatures (ca. 60–80 °C). For the complete approach, with electrolytic hydrogen renewable sources, PEM fuel cells can become one of the cleanest energy carriers. This is because water is the final product of such energy conversion systems. Currently, Nafion™ membranes are regularly used as hydrogen barriers in these fuel cells.

A Proton exchange membrane

Sufficient hydrogen gas supply is crucial for practical application of the PEMFC systems. Currently, expensive high-pressure tanks (70 MPa) are state-of-the-art for hydrogen storage. Besides cost, there are other drawbacks such as portability and safety. In order to address these issues, alternative hydrogen storage materials have been extensively investigated. For example, metal hydrides and organic hydride materials, can fix and release hydrogen via covalent bonding.

Now, Dr. Junpei Miyake and colleagues of the University of Yamanashi, Japan, have proposed an “all-polymer” rechargeable PEMFC system (RCFC). The work has been published in Nature Communications Chemistry. Their strategy was to apply a hydrogen-storage polymer (HSP) sheet (a solid-state organic hydride) as a hydrogen-storage medium inside the fuel cell. With this approach, the issues like toxicity, flammability and volatility as well as concerns related to other components such as the fuel reservoir, feed pump and vaporizer were solved. The HSP structure is based on fluorenol/fluorenone groups that take over hydrogen-storage functionality.

In order to test the performance of their HSP-based rechargeable fuel cell, the scientists attached the HSP sheet of the membrane electrode to the catalyst layer of the anode. At the same time, the cathode side was operated as in a regular PEMFC. The researchers reported that an iridium catalyst has been applied to the inside of the HSP sheet to improve the hydrogen-releasing and fixing processes.

Fuel cell operation, cycle performance and durability were tested using cycles of 6 periodic steps. At first, hydrogen was infused into HSP sheet for 2 h, followed by nitrogen gas flushing to remove hydrogen from the anode. Then, heating of the cell up to 80°C to initiated hydrogen release from the HSP sheet. Together with oxygen gas supplied to the cathode side the fuel cell produced constant electrical current.

The team demonstrated that their HSP sheet released 20%, 33%, 51%, or 96% of the total fixed hydrogen gas in 20, 30, 60, or 360 min, respectively. The temperature was 80°C in the presence of the iridium catalyst. Also, the iridium catalyst could absorb up to 58 mol% hydrogen, which was considerably lower than that stored in the HSP. The maximum operation time was approximately 10.2 s / mgHSP (ca. 509 s for 50 mg of HSP) at a constant current density of 1 mA / cm2. The RCFCs reached cycleability of least 50 cycles. In addition, the utilization of a gas impermeable sulfonated poly-phenylene membrane (SPP-QP, another type of PEM) turned out to be a good strategy to enhance the opration time of the RCFC.

The advantageous features of the reported RCFC system include better safety, easier handling and lower weight. These are perfect for example in mobile application such as fuel cell vehicles. However, for the improvement of the RCFC performance, hydrogen storage capacity and kinetics (H2-releasing/fixing reactions) as well as catalyst stability need further improvements.

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Faster photoelectrical hydrogen

Achieving high current densities while maintaining high energy efficiency is one of the biggest challenges in improving photoelectrochemical devices. Higher current densities accelerate the production of hydrogen and other electrochemical fuels.

Now a compact, solar-powered, hydrogen-producing device has been developed that provides the fuel at record speed. In the journal Nature Energy, the researchers around Saurabh Tembhurne describe a concept that allows capturing concentrated solar radiation (up to 474 kW/m²) by thermal integration, mass transport optimization and better electronics between the photoabsorber and the electrocatalyst.

The research group of the Swiss Federal Institute of Technology in Lausanne (EPFL) calculated the maximum increase in theoretical efficiency. Then, they experimentally verified the calculated values ​​using a photoabsorber and an iridium-ruthenium oxide-platinum based electrocatalyst. The electrocatalyst reached a current density greater than 0.88 A/cm². The calculated conversion efficiency of solar energy into hydrogen was more than 15%. The system was stable under various conditions for more than two hours. Next, the researchers want to scale their system.

The produced hydrogen can be used in fuel cells for power generation, which is why the developed system is suitable for energy storage. The hydrogen-powered generation of electricity emits only pure water. However, the clean and fast production of hydrogen is still a challenge. In the photoelectric method, materials similar to those of solar modules were used. The electrolytes were based on water in the new system, although ammonia would also be conceivable. Sunlight reaching these materials triggers a reaction in which water is split into oxygen and hydrogen. So far, however, all photoelectric methods could not be used on an industrial scale.

2 H2O → 2 H2 + O2; ∆G°’ = +237 kJ/mol (H2)

The newly developed system absorbed more than 400 times the amount of solar energy that normally shines on a given area. The researchers used high-power lamps to provide the necessary “solar energy”. Existing solar systems concentrate solar energy to a similar degree with the help of mirrors or lenses. The waste heat is used to accelerate the reaction.

The team predicts that the test equipment, with a footprint of approximately 5 cm, can produce an estimated 47 liters of hydrogen gas in six hours of sunshine. This is the highest rate per area for such solar powered electrochemical systems. At Frontis Energy we hope to be able to test and offer this system soon.

(Photo: Wikipedia)