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Researchers devise seawater-resilient bipolar membrane electrolyzer for turning seawater into hydrogen

Researchers at the Department of Energy’s SLAC National Accelerator Laboratory and Stanford University with collaborators at the University of Oregon and Manchester Metropolitan University have developed a seawater-resilient bipolar membrane electrolyzer. The design proved successful in generating hydrogen gas without producing large amounts of harmful byproducts.

The results of their study, published in Joule, could help advance efforts to produce low-carbon fuels.

Generation of H2 and O2 from untreated water sources represents a promising alternative to ultrapure water required in contemporary proton exchange membrane-based electrolysis. Bipolar membrane-based devices, often used in electrodialysis and CO2 electrolysis, facilitate impure water electrolysis via the simultaneous mediation of ion transport and enforcement of advantageous microenvironments. Herein, we report their application in direct seawater electrolysis; we show that upon introduction of ionic species such as Na+ and Cl from seawater, bipolar membrane electrolyzers limit the oxidation of Cl to corrosive OCl at the anode to a Faradaic efficiency (FE) of 0.005%, while proton exchange membrane electrolyzers under comparable operating conditions exhibit up to 10% FE to Cl oxidation. The effective mitigation of Cl oxidation by bipolar membrane electrolyzers underpins their ability to enable longer-term seawater electrolysis than proton exchange membrane assemblies by a factor of 140, suggesting a path to durable seawater electrolysis.

—Marin et al.

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The team started their design by controlling the most harmful element to the seawater system—chloride—said Joseph Perryman, a SLAC and Stanford postdoctoral researcher.

IMG_0129

A representation of the team’s bipolar membrane system that converts seawater into hydrogen gas. (Nina Fujikawa/SLAC National Accelerator Laboratory)


There are many reactive species in seawater that can interfere with the water-to-hydrogen reaction, and the sodium chloride that makes seawater salty is one of the main culprits. In particular, chloride that gets to the anode and oxidizes will reduce the lifetime of an electrolysis system and can actually become unsafe due to the toxic nature of the oxidation products that include molecular chlorine and bleach.

—Joseph Perryman

The bipolar membrane in the experiment allows access to the conditions needed to make hydrogen gas and mitigates chloride from getting to the reaction center.

An ideal membrane system performs three primary functions: separates hydrogen and oxygen gases from seawater; helps move only the useful hydrogen and hydroxide ions while restricting other seawater ions; and helps prevent undesired reactions. Capturing all three of these functions together is hard, and the team’s research is targeted toward exploring systems that can efficiently combine all three of these needs.

Specifically in their experiment, protons, which were the positive hydrogen ions, passed through one of the membrane layers to a place where they could be collected and turned into hydrogen gas by interacting with a negatively charged electrode. The second membrane in the system allowed only negative ions, such as chloride, to travel through.

As an additional backstop, one membrane layer contained negatively charged groups that were fixed to the membrane, which made it harder for other negatively charged ions, such as chloride, to move to places where they shouldn’t be, said Daniela Marin, a Stanford graduate student in chemical engineering and co-author. The negatively-charged membrane proved to be highly efficient in blocking almost all of the chloride ions in the team’s experiments, and their system operated without generating toxic byproducts such as bleach and chlorine.

Along with designing a seawater-to-hydrogen membrane system, the study also provided a better general understanding of how seawater ions moved through membranes, the researchers said. This knowledge could help scientists design stronger membranes for other applications as well, such as producing oxygen gas.

Next, the team plans to improve their electrodes and membranes by building them with materials that are more abundant and easily mined. This design improvement could make the electrolysis system easier to scale to a size needed to generate hydrogen for energy intensive activities, like the transportation sector, the team said.

The researchers also hope to take their electrolysis cells to SLAC’s Stanford Synchrotron Radiation Lightsource (SSRL), where they can study the atomic structure of catalysts and membranes using the facility’s intense X-rays.­­

This project is supported by the US Office of Naval Research; the Stanford Doerr School of Sustainability Accelerator; the DOE’s Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division through the SUNCAT Center for Interface Science and Catalysis, a SLAC-Stanford joint institute; and the DOE’s Energy Efficiency and Renewable Energy Fuel Cell Technologies Office.

Resources

  • D.H. Marin, J.T. Perryman et al. (2023) “Hydrogen production with seawater-resilient bipolar membrane electrolyzers”, Joule doi: 10.1016/j.joule.2023.03.005

Comments

Davemart

With apologies to those who are up to speed on developments in hydrogen technology, I thought it might be handy for some to point out why this may be important.

In the North sea, the idea is to produce hydrogen where the wind farms are, or on the coast adjacent to them where they are close inshore, then transport the hydrogen largely using repurposed NG pipelines which reduces the expence, so obviously using seawater is great if it can be done.

In another area, the Arabian Gulf, using seawater and their plentiful solar resources would be very helpful, although estimates are that if desalination has to be done, the cost is easily affordable:

https://www.greencarcongress.com/2021/08/20210830-namibia.html

Presumably it might be handy in the Gulf of Mexico too, but I am less familiar with the state of play there, so leave comments on that to others.

mahonj

Anyone know if it will be cheaper to make H2 from solar in sunny places or wind in windy (probably offshore) places?
Especially now since the 0% "free money" of the last few years has ended.

Davemart

Jim:

Offshore wind is still expensive relative to onshore, in spite of its usually higher utilisation factor, so my guess is that solar is normally cheaper.

But best is to combine the two, as when it ain't sunny, it is often windy, and vice versa, so capacity factors for the electrolysers and the rest of the gear increase.

Fortunately there are areas which have both, and some of them even low cost onshore wind.

Morocco springs to mind as one such, but there are a number of examples, often also near the coast for convenient shipment of the ammonia or whatever derived from hydrogen.

Rapidly falling electrolyser costs mean that capacity factors are becoming less important.

Jer

Often, the validity of these projects gets lost in the overall important priorities of the culture, region, and greater (valid) issues of the world itself. What might those priorities be, so that some kind of plan can be formalized, so that we are not scrambling and flailing about in a jungle of endless possibilities without reliable resources, proven technology, and 'buy in' from the local sources/ consumers (by decreasing importance):
1. Energy use or its manufacture should not obviously and measurably deteriorate human health at or above standards that show realtime physical damage in large populated areas.
2. Maintain the current energy capacity and reliability (and pricing) - whether it is a developing country or Times Square. No one should have to put up with unreliable power or unexpectedly spiking prices. This may be due to aging/ poorly-maintained infrastructure, poor planning on upgrades or new tech, etc. As an example, California should not have to put up with brown outs due to poor distribution and local disasters. Germany should not have to put up with spiking pricing (before Ukraine) due to poor planning from intermittent sources and anti-nuclear rhetoric.
3. Economic growth is crucial to social development and greater political stability; energy capacity and affordability should increase (at least) in kind. No one should have to diminish their lifestyle choices or pursue personal austerity or subjugate themselves to political values so as to minimize energy usage.
4. Energy use or its manufacture should not obviously and measurably deteriorate human health at or above standards that show realtime physical damage or proven long-term disability in local settings when there are other options. Older coal production without scrubbers or similar appears to still be a major issue in local areas. Many types of domestic combustion (wood, char) such as in developing countries is unacceptable.
5. Energy use or its manufacture should not obviously and measurably deteriorate environmental infrastructure and other natural features when there are other options.
6. Energy use or its manufacture should not obviously and measurably increase carbon intensity levels within definable service life cycles when there are other options.
7. Energy infrastructure inter-changeability, cross-border distribution, and improving export/import markets is helpful to development and improved economics; likely with more predictable capacity and affordability.

I'm not sure that this H2 article ticks any of the top 3 or 4 likely priorities.

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