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Bubble findings could unlock better electrode and electrolyzer designs
Industrial electrochemical processes that use electrodes to produce fuels and chemical products are hampered by the formation of bubbles that block parts of the electrode surface, reducing the area available for the active reaction. Such blockage reduces the performance of the electrodes by anywhere from 10 to 25 percent.
But new research reveals a decades-long misunderstanding about the extent of that interference. The findings show exactly how the blocking effect works and could lead to new ways of designing electrode surfaces to minimize inefficiencies in these widely used electrochemical processes.
It has long been assumed that the entire area of the electrode shadowed by each bubble would be effectively inactivated. But it turns out that a much smaller area — roughly the area where the bubble actually contacts the surface — is blocked from its electrochemical activity. The new insights could lead directly to new ways of patterning the surfaces to minimize the contact area and improve overall efficiency.
The findings are reported today in the journal Nanoscale, in a paper by recent MIT graduate Jack Lake PhD ’23, graduate student Simon Rufer, professor of mechanical engineering Kripa Varanasi, research scientist Ben Blaiszik, and six others at the University of Chicago and Argonne National Laboratory. The team has made available an open-source, AI-based software tool that engineers and scientists can now use to automatically recognize and quantify bubbles formed on a given surface, as a first step toward controlling the electrode material’s properties.
Gas-evolving electrodes, often with catalytic surfaces that promote chemical reactions, are used in a wide variety of processes, including the production of “green” hydrogen without the use of fossil fuels, carbon-capture processes that can reduce greenhouse gas emissions, aluminum production, and the chlor-alkali process that is used to make widely used chemical products.
These are very widespread processes. The chlor-alkali process alone accounts for 2 percent of all U.S. electricity usage; aluminum production accounts for 3 percent of global electricity; and both carbon capture and hydrogen production are likely to grow rapidly in coming years as the world strives to meet greenhouse-gas reduction targets. So, the new findings could make a real difference, Varanasi says.
“Our work demonstrates that engineering the contact and growth of bubbles on electrodes can have dramatic effects” on how bubbles form and how they leave the surface, he says. “The knowledge that the area under bubbles can be significantly active ushers in a new set of design rules for high-performance electrodes to avoid the deleterious effects of bubbles.”
“The broader literature built over the last couple of decades has suggested that not only that small area of contact but the entire area under the bubble is passivated,” Rufer says. The new study reveals “a significant difference between the two models because it changes how you would develop and design an electrode to minimize these losses.”
To test and demonstrate the implications of this effect, the team produced different versions of electrode surfaces with patterns of dots that nucleated and trapped bubbles at different sizes and spacings. They were able to show that surfaces with widely spaced dots promoted large bubble sizes but only tiny areas of surface contact, which helped to make clear the difference between the expected and actual effects of bubble coverage.
Developing the software to detect and quantify bubble formation was necessary for the team’s analysis, Rufer explains. “We wanted to collect a lot of data and look at a lot of different electrodes and different reactions and different bubbles, and they all look slightly different,” he says. Creating a program that could deal with different materials and different lighting and reliably identify and track the bubbles was a tricky process, and machine learning was key to making it work, he says.
Using that tool, he says, they were able to collect “really significant amounts of data about the bubbles on a surface, where they are, how big they are, how fast they’re growing, all these different things.” The tool is now freely available for anyone to use via the GitHub repository.
By using that tool to correlate the visual measures of bubble formation and evolution with electrical measurements of the electrode’s performance, the researchers were able to disprove the accepted theory and to show that only the area of direct contact is affected. Videos further proved the point, revealing new bubbles actively evolving directly under parts of a larger bubble.
The researchers developed a very general methodology that can be applied to characterize and understand the impact of bubbles on any electrode or catalyst surface. They were able to quantify the bubble passivation effects in a new performance metric they call BECSA (Bubble-induced electrochemically active surface), as opposed to ECSA (electrochemically active surface area), that is used in the field. “The BECSA metric was a concept we defined in an earlier study but did not have an effective method to estimate until this work,” says Varanasi.
The knowledge that the area under bubbles can be significantly active ushers in a new set of design rules for high-performance electrodes. This means that electrode designers should seek to minimize bubble contact area rather than simply bubble coverage, which can be achieved by controlling the morphology and chemistry of the electrodes. Surfaces engineered to control bubbles can not only improve the overall efficiency of the processes and thus reduce energy use, they can also save on upfront materials costs. Many of these gas-evolving electrodes are coated with catalysts made of expensive metals like platinum or iridium, and the findings from this work can be used to engineer electrodes to reduce material wasted by reaction-blocking bubbles.
Varanasi says that “the insights from this work could inspire new electrode architectures that not only reduce the usage of precious materials, but also improve the overall electrolyzer performance,” both of which would provide large-scale environmental benefits.
The research team included Jim James, Nathan Pruyne, Aristana Scourtas, Marcus Schwarting, Aadit Ambalkar, Ian Foster, and Ben Blaiszik at the University of Chicago and Argonne National Laboratory. The work was supported by the U.S. Department of Energy under the ARPA-E program.
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Solar-powered desalination system requires no extra batteries
MIT engineers have built a new desalination system that runs with the rhythms of the sun.
The solar-powered system removes salt from water at a pace that closely follows changes in solar energy. As sunlight increases through the day, the system ramps up its desalting process and automatically adjusts to any sudden variation in sunlight, for example by dialing down in response to a passing cloud or revving up as the skies clear.
Because the system can quickly react to subtle changes in sunlight, it maximizes the utility of solar energy, producing large quantities of clean water despite variations in sunlight throughout the day. In contrast to other solar-driven desalination designs, the MIT system requires no extra batteries for energy storage, nor a supplemental power supply, such as from the grid.
The engineers tested a community-scale prototype on groundwater wells in New Mexico over six months, working in variable weather conditions and water types. The system harnessed on average over 94 percent of the electrical energy generated from the system’s solar panels to produce up to 5,000 liters of water per day despite large swings in weather and available sunlight.
“Conventional desalination technologies require steady power and need battery storage to smooth out a variable power source like solar. By continually varying power consumption in sync with the sun, our technology directly and efficiently uses solar power to make water,” says Amos Winter, the Germeshausen Professor of Mechanical Engineering and director of the K. Lisa Yang Global Engineering and Research (GEAR) Center at MIT. “Being able to make drinking water with renewables, without requiring battery storage, is a massive grand challenge. And we’ve done it.”
The system is geared toward desalinating brackish groundwater — a salty source of water that is found in underground reservoirs and is more prevalent than fresh groundwater resources. The researchers see brackish groundwater as a huge untapped source of potential drinking water, particularly as reserves of fresh water are stressed in parts of the world. They envision that the new renewable, battery-free system could provide much-needed drinking water at low costs, especially for inland communities where access to seawater and grid power are limited.
“The majority of the population actually lives far enough from the coast, that seawater desalination could never reach them. They consequently rely heavily on groundwater, especially in remote, low-income regions. And unfortunately, this groundwater is becoming more and more saline due to climate change,” says Jonathan Bessette, MIT PhD student in mechanical engineering. “This technology could bring sustainable, affordable clean water to underreached places around the world.”
The researchers report details the new system in a paper appearing today in Nature Water. The study’s co-authors are Bessette, Winter, and staff engineer Shane Pratt.
Pump and flow
The new system builds on a previous design, which Winter and his colleagues, including former MIT postdoc Wei He, reported earlier this year. That system aimed to desalinate water through “flexible batch electrodialysis.”
Electrodialysis and reverse osmosis are two of the main methods used to desalinate brackish groundwater. With reverse osmosis, pressure is used to pump salty water through a membrane and filter out salts. Electrodialysis uses an electric field to draw out salt ions as water is pumped through a stack of ion-exchange membranes.
Scientists have looked to power both methods with renewable sources. But this has been especially challenging for reverse osmosis systems, which traditionally run at a steady power level that’s incompatible with naturally variable energy sources such as the sun.
Winter, He, and their colleagues focused on electrodialysis, seeking ways to make a more flexible, “time-variant” system that would be responsive to variations in renewable, solar power.
In their previous design, the team built an electrodialysis system consisting of water pumps, an ion-exchange membrane stack, and a solar panel array. The innovation in this system was a model-based control system that used sensor readings from every part of the system to predict the optimal rate at which to pump water through the stack and the voltage that should be applied to the stack to maximize the amount of salt drawn out of the water.
When the team tested this system in the field, it was able to vary its water production with the sun’s natural variations. On average, the system directly used 77 percent of the available electrical energy produced by the solar panels, which the team estimated was 91 percent more than traditionally designed solar-powered electrodialysis systems.
Still, the researchers felt they could do better.
“We could only calculate every three minutes, and in that time, a cloud could literally come by and block the sun,” Winter says. “The system could be saying, ‘I need to run at this high power.’ But some of that power has suddenly dropped because there’s now less sunlight. So, we had to make up that power with extra batteries.”
Solar commands
In their latest work, the researchers looked to eliminate the need for batteries, by shaving the system’s response time to a fraction of a second. The new system is able to update its desalination rate, three to five times per second. The faster response time enables the system to adjust to changes in sunlight throughout the day, without having to make up any lag in power with additional power supplies.
The key to the nimbler desalting is a simpler control strategy, devised by Bessette and Pratt. The new strategy is one of “flow-commanded current control,” in which the system first senses the amount of solar power that is being produced by the system’s solar panels. If the panels are generating more power than the system is using, the controller automatically “commands” the system to dial up its pumping, pushing more water through the electrodialysis stacks. Simultaneously, the system diverts some of the additional solar power by increasing the electrical current delivered to the stack, to drive more salt out of the faster-flowing water.
“Let’s say the sun is rising every few seconds,” Winter explains. “So, three times a second, we’re looking at the solar panels and saying, ‘Oh, we have more power — let’s bump up our flow rate and current a little bit.’ When we look again and see there’s still more excess power, we’ll up it again. As we do that, we’re able to closely match our consumed power with available solar power really accurately, throughout the day. And the quicker we loop this, the less battery buffering we need.”
The engineers incorporated the new control strategy into a fully automated system that they sized to desalinate brackish groundwater at a daily volume that would be enough to supply a small community of about 3,000 people. They operated the system for six months on several wells at the Brackish Groundwater National Desalination Research Facility in Alamogordo, New Mexico. Throughout the trial, the prototype operated under a wide range of solar conditions, harnessing over 94 percent of the solar panel’s electrical energy, on average, to directly power desalination.
“Compared to how you would traditionally design a solar desal system, we cut our required battery capacity by almost 100 percent,” Winter says.
The engineers plan to further test and scale up the system in hopes of supplying larger communities, and even whole municipalities, with low-cost, fully sun-driven drinking water.
“While this is a major step forward, we’re still working diligently to continue developing lower cost, more sustainable desalination methods,” Bessette says.
“Our focus now is on testing, maximizing reliability, and building out a product line that can provide desalinated water using renewables to multiple markets around the world,” Pratt adds.
The team will be launching a company based on their technology in the coming months.
This research was supported in part by the National Science Foundation, the Julia Burke Foundation, and the MIT Morningside Academy of Design. This work was additionally supported in-kind by Veolia Water Technologies and Solutions and Xylem Goulds.
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