More stories

  • in

    Strengthening electron-triggered light emission

    The way electrons interact with photons of light is a key part of many modern technologies, from lasers to solar panels to LEDs. But the interaction is inherently a weak one because of a major mismatch in scale: A wavelength of visible light is about 1,000 times larger than an electron, so the way the two things affect each other is limited by that disparity.

    Now, researchers at MIT and elsewhere have come up with an innovative way to make much stronger interactions between photons and electrons possible, in the process producing a hundredfold increase in the emission of light from a phenomenon called Smith-Purcell radiation. The finding has potential implications for both commercial applications and fundamental scientific research, although it will require more years of research to make it practical.

    The findings are reported today in the journal Nature, in a paper by MIT postdocs Yi Yang (now an assistant professor at the University of Hong Kong) and Charles Roques-Carmes, MIT professors Marin Soljačić and John Joannopoulos, and five others at MIT, Harvard University, and Technion-Israel Institute of Technology.

    In a combination of computer simulations and laboratory experiments, the team found that using a beam of electrons in combination with a specially designed photonic crystal — a slab of silicon on an insulator, etched with an array of nanometer-scale holes — they could theoretically predict stronger emission by many orders of magnitude than would ordinarily be possible in conventional Smith-Purcell radiation. They also experimentally recorded a one hundredfold increase in radiation in their proof-of-concept measurements.

    Unlike other approaches to producing sources of light or other electromagnetic radiation, the free-electron-based method is fully tunable — it can produce emissions of any desired wavelength, simply by adjusting the size of the photonic structure and the speed of the electrons. This may make it especially valuable for making sources of emission at wavelengths that are difficult to produce efficiently, including terahertz waves, ultraviolet light, and X-rays.

    The team has so far demonstrated the hundredfold enhancement in emission using a repurposed electron microscope to function as an electron beam source. But they say that the basic principle involved could potentially enable far greater enhancements using devices specifically adapted for this function.

    The approach is based on a concept called flatbands, which have been widely explored in recent years for condensed matter physics and photonics but have never been applied to affecting the basic interaction of photons and free electrons. The underlying principle involves the transfer of momentum from the electron to a group of photons, or vice versa. Whereas conventional light-electron interactions rely on producing light at a single angle, the photonic crystal is tuned in such a way that it enables the production of a whole range of angles.

    The same process could also be used in the opposite direction, using resonant light waves to propel electrons, increasing their velocity in a way that could potentially be harnessed to build miniaturized particle accelerators on a chip. These might ultimately be able to perform some functions that currently require giant underground tunnels, such as the 30-kilometer-wide Large Hadron Collider in Switzerland.

    “If you could actually build electron accelerators on a chip,” Soljačić says, “you could make much more compact accelerators for some of the applications of interest, which would still produce very energetic electrons. That obviously would be huge. For many applications, you wouldn’t have to build these huge facilities.”

    The new system could also potentially provide a highly controllable X-ray beam for radiotherapy purposes, Roques-Carmes says.

    And the system could be used to generate multiple entangled photons, a quantum effect that could be useful in the creation of quantum-based computational and communications systems, the researchers say. “You can use electrons to couple many photons together, which is a considerably hard problem if using a purely optical approach,” says Yang. “That is one of the most exciting future directions of our work.”

    Much work remains to translate these new findings into practical devices, Soljačić cautions. It may take some years to develop the necessary interfaces between the optical and electronic components and how to connect them on a single chip, and to develop the necessary on-chip electron source producing a continuous wavefront, among other challenges.

    “The reason this is exciting,” Roques-Carmes adds, “is because this is quite a different type of source.” While most technologies for generating light are restricted to very specific ranges of color or wavelength, and “it’s usually difficult to move that emission frequency. Here it’s completely tunable. Simply by changing the velocity of the electrons, you can change the emission frequency. … That excites us about the potential of these sources. Because they’re different, they offer new types of opportunities.”

    But, Soljačić concludes, “in order for them to become truly competitive with other types of sources, I think it will require some more years of research. I would say that with some serious effort, in two to five years they might start competing in at least some areas of radiation.”

    The research team also included Steven Kooi at MIT’s Institute for Soldier Nanotechnologies, Haoning Tang and Eric Mazur at Harvard University, Justin Beroz at MIT, and Ido Kaminer at Technion-Israel Institute of Technology. The work was supported by the U.S. Army Research Office through the Institute for Soldier Nanotechnologies, the U.S. Air Force Office of Scientific Research, and the U.S. Office of Naval Research. More

  • in

    Team creates map for production of eco-friendly metals

    In work that could usher in more efficient, eco-friendly processes for producing important metals like lithium, iron, and cobalt, researchers from MIT and the SLAC National Accelerator Laboratory have mapped what is happening at the atomic level behind a particularly promising approach called metal electrolysis.

    By creating maps for a wide range of metals, they not only determined which metals should be easiest to produce using this approach, but also identified fundamental barriers behind the efficient production of others. As a result, the researchers’ map could become an important design tool for optimizing the production of all these metals.

    The work could also aid the development of metal-air batteries, cousins of the lithium-ion batteries used in today’s electric vehicles.

    Most of the metals key to society today are produced using fossil fuels. These fuels generate the high temperatures necessary to convert the original ore into its purified metal. But that process is a significant source of greenhouse gases — steel alone accounts for some 7 percent of carbon dioxide emissions globally. As a result, researchers from around the world are working to identify more eco-friendly ways for the production of metals.

    One promising approach is metal electrolysis, in which a metal oxide, the ore, is zapped with electricity to create pure metal with oxygen as the byproduct. That is the reaction explored at the atomic level in new research reported in the April 8 issue of the journal Chemistry of Materials.

    Donald Siegel is department chair and professor of mechanical engineering at the University of Texas at Austin. Says Siegel, who was not involved in the Chemistry of Materials study: “This work is an important contribution to improving the efficiency of metal production from metal oxides. It clarifies our understanding of low-carbon electrolysis processes by tracing the underlying thermodynamics back to elementary metal-oxygen interactions. I expect that this work will aid in the creation of design rules that will make these industrially important processes less reliant on fossil fuels.”

    Yang Shao-Horn, the JR East Professor of Engineering in MIT’s Department of Materials Science and Engineering (DMSE) and Department of Mechanical Engineering, is a leader of the current work, with Michal Bajdich of SLAC.

    “Here we aim to establish some basic understanding to predict the efficiency of electrochemical metal production and metal-air batteries from examining computed thermodynamic barriers for the conversion between metal and metal oxides,” says Shao-Horn, who is on the research team for MIT’s new Center for Electrification and Decarbonization of Industry, a winner of the Institute’s first-ever Climate Grand Challenges competition. Shao-Horn is also affiliated with MIT’s Materials Research Laboratory and Research Laboratory of Electronics.

    In addition to Shao-Horn and Bajdich, other authors of the Chemistry of Materials paper are Jaclyn R. Lunger, first author and a DMSE graduate student; mechanical engineering senior Naomi Lutz; and DMSE graduate student Jiayu Peng.

    Other applications

    The work could also aid in developing metal-air batteries such as lithium-air, aluminum-air, and zinc-air batteries. These cousins of the lithium-ion batteries used in today’s electric vehicles have the potential to electrify aviation because their energy densities are much higher. However, they are not yet on the market due to a variety of problems including inefficiency.

    Charging metal-air batteries also involves electrolysis. As a result, the new atomic-level understanding of these reactions could not only help engineers develop efficient electrochemical routes for metal production, but also design more efficient metal-air batteries.

    Learning from water splitting

    Electrolysis is also used to split water into oxygen and hydrogen, which stores the resulting energy. That hydrogen, in turn, could become an eco-friendly alternative to fossil fuels. Since much more is known about water electrolysis, the focus of Bajdich’s work at SLAC, than the electrolysis of metal oxides, the team compared the two processes for the first time.

    The result: “Slowly, we uncovered the elementary steps involved in metal electrolysis,” says Bajdich. The work was challenging, says Lunger, because “it was unclear to us what those steps are. We had to figure out how to get from A to B,” or from a metal oxide to metal and oxygen.

    All of the work was conducted with supercomputer simulations. “It’s like a sandbox of atoms, and then we play with them. It’s a little like Legos,” says Bajdich. More specifically, the team explored different scenarios for the electrolysis of several metals. Each involved different catalysts, molecules that boost the speed of a reaction.

    Says Lunger, “To optimize the reaction, you want to find the catalyst that makes it most efficient.” The team’s map is essentially a guide for designing the best catalysts for each different metal.

    What’s next? Lunger noted that the current work focused on the electrolysis of pure metals. “I’m interested in seeing what happens in more complex systems involving multiple metals. Can you make the reaction more efficient if there’s sodium and lithium present, or cadmium and cesium?”

    This work was supported by a U.S. Department of Energy Office of Science Graduate Student Research award. It was also supported by an MIT Energy Initiative fellowship, the Toyota Research Institute through the Accelerated Materials Design and Discovery Program, the Catalysis Science Program of Department of Energy, Office of Basic Energy Sciences, and by the Differentiate Program through the U.S. Advanced Research Projects Agency — Energy.  More

  • in

    From seawater to drinking water, with the push of a button

    MIT researchers have developed a portable desalination unit, weighing less than 10 kilograms, that can remove particles and salts to generate drinking water.

    The suitcase-sized device, which requires less power to operate than a cell phone charger, can also be driven by a small, portable solar panel, which can be purchased online for around $50. It automatically generates drinking water that exceeds World Health Organization quality standards. The technology is packaged into a user-friendly device that runs with the push of one button.

    Unlike other portable desalination units that require water to pass through filters, this device utilizes electrical power to remove particles from drinking water. Eliminating the need for replacement filters greatly reduces the long-term maintenance requirements.

    This could enable the unit to be deployed in remote and severely resource-limited areas, such as communities on small islands or aboard seafaring cargo ships. It could also be used to aid refugees fleeing natural disasters or by soldiers carrying out long-term military operations.

    “This is really the culmination of a 10-year journey that I and my group have been on. We worked for years on the physics behind individual desalination processes, but pushing all those advances into a box, building a system, and demonstrating it in the ocean, that was a really meaningful and rewarding experience for me,” says senior author Jongyoon Han, a professor of electrical engineering and computer science and of biological engineering, and a member of the Research Laboratory of Electronics (RLE).

    Joining Han on the paper are first author Junghyo Yoon, a research scientist in RLE; Hyukjin J. Kwon, a former postdoc; SungKu Kang, a postdoc at Northeastern University; and Eric Brack of the U.S. Army Combat Capabilities Development Command (DEVCOM). The research has been published online in Environmental Science and Technology.

    Play video

    Filter-free technology

    Commercially available portable desalination units typically require high-pressure pumps to push water through filters, which are very difficult to miniaturize without compromising the energy-efficiency of the device, explains Yoon.

    Instead, their unit relies on a technique called ion concentration polarization (ICP), which was pioneered by Han’s group more than 10 years ago. Rather than filtering water, the ICP process applies an electrical field to membranes placed above and below a channel of water. The membranes repel positively or negatively charged particles — including salt molecules, bacteria, and viruses — as they flow past. The charged particles are funneled into a second stream of water that is eventually discharged.

    The process removes both dissolved and suspended solids, allowing clean water to pass through the channel. Since it only requires a low-pressure pump, ICP uses less energy than other techniques.

    But ICP does not always remove all the salts floating in the middle of the channel. So the researchers incorporated a second process, known as electrodialysis, to remove remaining salt ions.

    Yoon and Kang used machine learning to find the ideal combination of ICP and electrodialysis modules. The optimal setup includes a two-stage ICP process, with water flowing through six modules in the first stage then through three in the second stage, followed by a single electrodialysis process. This minimized energy usage while ensuring the process remains self-cleaning.

    “While it is true that some charged particles could be captured on the ion exchange membrane, if they get trapped, we just reverse the polarity of the electric field and the charged particles can be easily removed,” Yoon explains.

    They shrunk and stacked the ICP and electrodialysis modules to improve their energy efficiency and enable them to fit inside a portable device. The researchers designed the device for nonexperts, with just one button to launch the automatic desalination and purification process. Once the salinity level and the number of particles decrease to specific thresholds, the device notifies the user that the water is drinkable.

    The researchers also created a smartphone app that can control the unit wirelessly and report real-time data on power consumption and water salinity.

    Beach tests

    After running lab experiments using water with different salinity and turbidity (cloudiness) levels, they field-tested the device at Boston’s Carson Beach.

    Yoon and Kwon set the box near the shore and tossed the feed tube into the water. In about half an hour, the device had filled a plastic drinking cup with clear, drinkable water.

    “It was successful even in its first run, which was quite exciting and surprising. But I think the main reason we were successful is the accumulation of all these little advances that we made along the way,” Han says.

    The resulting water exceeded World Health Organization quality guidelines, and the unit reduced the amount of suspended solids by at least a factor of 10. Their prototype generates drinking water at a rate of 0.3 liters per hour, and requires only 20 watts of power per liter.

    “Right now, we are pushing our research to scale up that production rate,” Yoon says.

    One of the biggest challenges of designing the portable system was engineering an intuitive device that could be used by anyone, Han says.

    Yoon hopes to make the device more user-friendly and improve its energy efficiency and production rate through a startup he plans to launch to commercialize the technology.

    In the lab, Han wants to apply the lessons he’s learned over the past decade to water-quality issues that go beyond desalination, such as rapidly detecting contaminants in drinking water.

    “This is definitely an exciting project, and I am proud of the progress we have made so far, but there is still a lot of work to do,” he says.

    For example, while “development of portable systems using electro-membrane processes is an original and exciting direction in off-grid, small-scale desalination,” the effects of fouling, especially if the water has high turbidity, could significantly increase maintenance requirements and energy costs, notes Nidal Hilal, professor of engineering and director of the New York University Abu Dhabi Water research center, who was not involved with this research.

    “Another limitation is the use of expensive materials,” he adds. “It would be interesting to see similar systems with low-cost materials in place.”

    The research was funded, in part, by the DEVCOM Soldier Center, the Abdul Latif Jameel Water and Food Systems Lab (J-WAFS), the Experimental AI Postdoc Fellowship Program of Northeastern University, and the Roux AI Institute. More

  • in

    More sensitive X-ray imaging

    Scintillators are materials that emit light when bombarded with high-energy particles or X-rays. In medical or dental X-ray systems, they convert incoming X-ray radiation into visible light that can then be captured using film or photosensors. They’re also used for night-vision systems and for research, such as in particle detectors or electron microscopes.

    Researchers at MIT have now shown how one could improve the efficiency of scintillators by at least tenfold, and perhaps even a hundredfold, by changing the material’s surface to create certain nanoscale configurations, such as arrays of wave-like ridges. While past attempts to develop more efficient scintillators have focused on finding new materials, the new approach could in principle work with any of the existing materials.

    Though it will require more time and effort to integrate their scintillators into existing X-ray machines, the team believes that this method might lead to improvements in medical diagnostic X-rays or CT scans, to reduce dose exposure and improve image quality. In other applications, such as X-ray inspection of manufactured parts for quality control, the new scintillators could enable inspections with higher accuracy or at faster speeds.

    The findings are described today in the journal Science, in a paper by MIT doctoral students Charles Roques-Carmes and Nicholas Rivera; MIT professors Marin Soljacic, Steven Johnson, and John Joannopoulos; and 10 others.

    While scintillators have been in use for some 70 years, much of the research in the field has focused on developing new materials that produce brighter or faster light emissions. The new approach instead applies advances in nanotechnology to existing materials. By creating patterns in scintillator materials at a length scale comparable to the wavelengths of the light being emitted, the team found that it was possible to dramatically change the material’s optical properties.

    To make what they coined “nanophotonic scintillators,” Roques-Carmes says, “you can directly make patterns inside the scintillators, or you can glue on another material that would have holes on the nanoscale. The specifics depend on the exact structure and material.” For this research, the team took a scintillator and made holes spaced apart by roughly one optical wavelength, or about 500 nanometers (billionths of a meter).

    “The key to what we’re doing is a general theory and framework we have developed,” Rivera says. This allows the researchers to calculate the scintillation levels that would be produced by any arbitrary configuration of nanophotonic structures. The scintillation process itself involves a series of steps, making it complicated to unravel. The framework the team developed involves integrating three different types of physics, Roques-Carmes says. Using this system they have found a good match between their predictions and the results of their subsequent experiments.

    The experiments showed a tenfold improvement in emission from the treated scintillator. “So, this is something that might translate into applications for medical imaging, which are optical photon-starved, meaning the conversion of X-rays to optical light limits the image quality. [In medical imaging,] you do not want to irradiate your patients with too much of the X-rays, especially for routine screening, and especially for young patients as well,” Roques-Carmes says.

    “We believe that this will open a new field of research in nanophotonics,” he adds. “You can use a lot of the existing work and research that has been done in the field of nanophotonics to improve significantly on existing materials that scintillate.”

    “The research presented in this paper is hugely significant,” says Rajiv Gupta, chief of neuroradiology at Massachusetts General Hospital and an associate professor at Harvard Medical School, who was not associated with this work. “Nearly all detectors used in the $100 billion [medical X-ray] industry are indirect detectors,” which is the type of detector the new findings apply to, he says. “Everything that I use in my clinical practice today is based on this principle. This paper improves the efficiency of this process by 10 times. If this claim is even partially true, say the improvement is two times instead of 10 times, it would be transformative for the field!”

    Soljacic says that while their experiments proved a tenfold improvement in emission could be achieved in particular systems, by further fine-tuning the design of the nanoscale patterning, “we also show that you can get up to 100 times [improvement] in certain scintillator systems, and we believe we also have a path toward making it even better,” he says.

    Soljacic points out that in other areas of nanophotonics, a field that deals with how light interacts with materials that are structured at the nanometer scale, the development of computational simulations has enabled rapid, substantial improvements, for example in the development of solar cells and LEDs. The new models this team developed for scintillating materials could facilitate similar leaps in this technology, he says.

    Nanophotonics techniques “give you the ultimate power of tailoring and enhancing the behavior of light,” Soljacic says. “But until now, this promise, this ability to do this with scintillation was unreachable because modeling the scintillation was very challenging. Now, this work for the first time opens up this field of scintillation, fully opens it, for the application of nanophotonics techniques.” More generally, the team believes that the combination of nanophotonic and scintillators might ultimately enable higher resolution, reduced X-ray dose, and energy-resolved X-ray imaging.

    This work is “very original and excellent,” says Eli Yablonovitch, a professor of Electrical Engineering and Computer Sciences at the University of California at Berkeley, who was not associated with this research. “New scintillator concepts are very important in medical imaging and in basic research.”

    Yablonovitch adds that while the concept still needs to be proven in a practical device, he says that, “After years of research on photonic crystals in optical communication and other fields, it’s long overdue that photonic crystals should be applied to scintillators, which are of great practical importance yet have been overlooked” until this work.

    The research team included Ali Ghorashi, Steven Kooi, Yi Yang, Zin Lin, Justin Beroz, Aviram Massuda, Jamison Sloan, and Nicolas Romeo at MIT; Yang Yu at Raith America, Inc.; and Ido Kaminer at Technion in Israel. The work was supported, in part, by the U.S. Army Research Office and the U.S. Army Research Laboratory through the Institute for Soldier Nanotechnologies, by the Air Force Office of Scientific Research, and by a Mathworks Engineering Fellowship. More

  • in

    An energy-storage solution that flows like soft-serve ice cream

    Batteries made from an electrically conductive mixture the consistency of molasses could help solve a critical piece of the decarbonization puzzle. An interdisciplinary team from MIT has found that an electrochemical technology called a semisolid flow battery can be a cost-competitive form of energy storage and backup for variable renewable energy (VRE) sources such as wind and solar. The group’s research is described in a paper published in Joule.

    “The transition to clean energy requires energy storage systems of different durations for when the sun isn’t shining and the wind isn’t blowing,” says Emre Gençer, a research scientist with the MIT Energy Initiative (MITEI) and a member of the team. “Our work demonstrates that a semisolid flow battery could be a lifesaving as well as economical option when these VRE sources can’t generate power for a day or longer — in the case of natural disasters, for instance.”

    The rechargeable zinc-manganese dioxide (Zn-MnO2) battery the researchers created beat out other long-duration energy storage contenders. “We performed a comprehensive, bottom-up analysis to understand how the battery’s composition affects performance and cost, looking at all the trade-offs,” says Thaneer Malai Narayanan SM ’18, PhD ’21. “We showed that our system can be cheaper than others, and can be scaled up.”

    Narayanan, who conducted this work at MIT as part of his doctorate in mechanical engineering, is the lead author of the paper. Additional authors include Gençer, Yunguang Zhu, a postdoc in the MIT Electrochemical Energy Lab; Gareth McKinley, the School of Engineering Professor of Teaching Innovation and professor of mechanical engineering at MIT; and Yang Shao-Horn, the JR East Professor of Engineering, a professor of mechanical engineering and of materials science and engineering, and a member of the Research Laboratory of Electronics (RLE), who directs the MIT Electrochemical Energy Lab.

    Going with the flow

    In 2016, Narayanan began his graduate studies, joining the Electrochemical Energy Lab, a hotbed of research and exploration of solutions to mitigate climate change, which is centered on innovative battery chemistry and decarbonizing fuels and chemicals. One exciting opportunity for the lab: developing low- and no-carbon backup energy systems suitable for grid-scale needs when VRE generation flags.                                                  

    While the lab cast a wide net, investigating energy conversion and storage using solid oxide fuel cells, lithium-ion batteries, and metal-air batteries, among others, Narayanan took a particular interest in flow batteries. In these systems, two different chemical (electrolyte) solutions with either negative or positive ions are pumped from separate tanks, meeting across a membrane (called the stack). Here, the ion streams react, converting electrical energy to chemical energy — in effect, charging the battery. When there is demand for this stored energy, the solution gets pumped back to the stack to convert chemical energy into electrical energy again.

    The duration of time that flow batteries can discharge, releasing the stored electricity, is determined by the volume of positively and negatively charged electrolyte solutions streaming through the stack. In theory, as long as these solutions keep flowing, reacting, and converting the chemical energy to electrical energy, the battery systems can provide electricity.

    “For backup lasting more than a day, the architecture of flow batteries suggests they can be a cheap option,” says Narayanan. “You recharge the solution in the tanks from sun and wind power sources.” This renders the entire system carbon free.

    But while the promise of flow battery technologies has beckoned for at least a decade, the uneven performance and expense of materials required for these battery systems has slowed their implementation. So, Narayanan set out on an ambitious journey: to design and build a flow battery that could back up VRE systems for a day or more, storing and discharging energy with the same or greater efficiency than backup rivals; and to determine, through rigorous cost analysis, whether such a system could prove economically viable as a long-duration energy option.

    Multidisciplinary collaborators

    To attack this multipronged challenge, Narayanan’s project brought together, in his words, “three giants, scientists all well-known in their fields”:  Shao-Horn, who specializes in chemical physics and electrochemical science, and design of materials; Gençer, who creates detailed economic models of emergent energy systems at MITEI; and McKinley, an expert in rheology, the physics of flow. These three also served as his thesis advisors.

    “I was excited to work in such an interdisciplinary team, which offered a unique opportunity to create a novel battery architecture by designing charge transfer and ion transport within flowable semi-solid electrodes, and to guide battery engineering using techno-economics of such flowable batteries,” says Shao-Horn.

    While other flow battery systems in contention, such as the vanadium redox flow battery, offer the storage capacity and energy density to back up megawatt and larger power systems, they depend on expensive chemical ingredients that make them bad bets for long duration purposes. Narayanan was on the hunt for less-pricey chemical components that also feature rich energy potential.

    Through a series of bench experiments, the researchers came up with a novel electrode (electrical conductor) for the battery system: a mixture containing dispersed manganese dioxide (MnO2) particles, shot through with an electrically conductive additive, carbon black. This compound reacts with a conductive zinc solution or zinc plate at the stack, enabling efficient electrochemical energy conversion. The fluid properties of this battery are far removed from the watery solutions used by other flow batteries.

    “It’s a semisolid — a slurry,” says Narayanan. “Like thick, black paint, or perhaps a soft-serve ice cream,” suggests McKinley. The carbon black adds the pigment and the electric punch. To arrive at the optimal electrochemical mix, the researchers tweaked their formula many times.

    “These systems have to be able to flow under reasonable pressures, but also have a weak yield stress so that the active MnO2 particles don’t sink to the bottom of the flow tanks when the system isn’t being used, as well as not separate into a battery/oily clear fluid phase and a dense paste of carbon particles and MnO2,” says McKinley.

    This series of experiments informed the technoeconomic analysis. By “connecting the dots between composition, performance, and cost,” says Narayanan, he and Gençer were able to make system-level cost and efficiency calculations for the Zn-MnO2 battery.

    “Assessing the cost and performance of early technologies is very difficult, and this was an example of how to develop a standard method to help researchers at MIT and elsewhere,” says Gençer. “One message here is that when you include the cost analysis at the development stage of your experimental work, you get an important early understanding of your project’s cost implications.”

    In their final round of studies, Gençer and Narayanan compared the Zn-MnO2 battery to a set of equivalent electrochemical battery and hydrogen backup systems, looking at the capital costs of running them at durations of eight, 24, and 72 hours. Their findings surprised them: For battery discharges longer than a day, their semisolid flow battery beat out lithium-ion batteries and vanadium redox flow batteries. This was true even when factoring in the heavy expense of pumping the MnO2 slurry from tank to stack. “I was skeptical, and not expecting this battery would be competitive, but once I did the cost calculation, it was plausible,” says Gençer.

    But carbon-free battery backup is a very Goldilocks-like business: Different situations require different-duration solutions, whether an anticipated overnight loss of solar power, or a longer-term, climate-based disruption in the grid. “Lithium-ion is great for backup of eight hours and under, but the materials are too expensive for longer periods,” says Gençer. “Hydrogen is super expensive for very short durations, and good for very long durations, and we will need all of them.” This means it makes sense to continue working on the Zn-MnO2 system to see where it might fit in.

    “The next step is to take our battery system and build it up,” says Narayanan, who is working now as a battery engineer. “Our research also points the way to other chemistries that could be developed under the semi-solid flow battery platform, so we could be seeing this kind of technology used for energy storage in our lifetimes.”

    This research was supported by Eni S.p.A. through MITEI. Thaneer Malai Narayanan received an Eni-sponsored MIT Energy Fellowship during his work on the project. More

  • in

    Making catalytic surfaces more active to help decarbonize fuels and chemicals

    Electrochemical reactions that are accelerated using catalysts lie at the heart of many processes for making and using fuels, chemicals, and materials — including storing electricity from renewable energy sources in chemical bonds, an important capability for decarbonizing transportation fuels. Now, research at MIT could open the door to ways of making certain catalysts more active, and thus enhancing the efficiency of such processes.

    A new production process yielded catalysts that increased the efficiency of the chemical reactions by fivefold, potentially enabling useful new processes in biochemistry, organic chemistry, environmental chemistry, and electrochemistry. The findings are described today in the journal Nature Catalysis, in a paper by Yang Shao-Horn, an MIT professor of mechanical engineering and of materials science and engineering, and a member of the Research Lab of Electronics (RLE); Tao Wang, a postdoc in RLE; Yirui Zhang, a graduate student in the Department of Mechanical Engineering; and five others.

    The process involves adding a layer of what’s called an ionic liquid in between a gold or platinum catalyst and a chemical feedstock. Catalysts produced with this method could potentially enable much more efficient conversion of hydrogen fuel to power devices such as fuel cells, or more efficient conversion of carbon dioxide into fuels.

    “There is an urgent need to decarbonize how we power transportation beyond light-duty vehicles, how we make fuels, and how we make materials and chemicals,” says Shao-Horn, emphasizing the pressing call to reduce carbon emissions highlighted in the latest IPCC report on climate change. This new approach to enhancing catalytic activity could provide an important step in that direction, she says.

    Using hydrogen in electrochemical devices such as fuel cells is one promising approach to decarbonizing fields such as aviation and heavy-duty vehicles, and the new process may help to make such uses practical. At present, the oxygen reduction reaction that powers such fuel cells is limited by its inefficiency. Previous attempts to improve that efficiency have focused on choosing different catalyst materials or modifying their surface compositions and structure.

    In this research, however, instead of modifying the solid surfaces, the team added a thin layer in between the catalyst and the electrolyte, the active material that participates in the chemical reaction. The ionic liquid layer, they found, regulates the activity of protons that help to increase the rate of the chemical reactions taking place on the interface.

    Because there is a great variety of such ionic liquids to choose from, it’s possible to “tune” proton activity and the reaction rates to match the energetics needed for processes involving proton transfer, which can be used to make fuels and chemicals through reactions with oxygen.

    “The proton activity and the barrier for proton transfer is governed by the ionic liquid layer, and so there’s a great tuneability in terms of catalytic activity for reactions involving proton and electron transfer,” Shao-Horn says. And the effect is produced by a vanishingly thin layer of the liquid, just a few nanometers thick, above which is a much thicker layer of the liquid that is to undergo the reaction.

    “I think this concept is novel and important,” says Wang, the paper’s first author, “because people know the proton activity is important in many electrochemistry reactions, but it’s very challenging to study.” That’s because in a water environment, there are so many interactions between neighboring water molecules involved that it’s very difficult to separate out which reactions are taking place. By using an ionic liquid, whose ions can each only form a single bond with the intermediate material, it became possible to study the reactions in detail, using infrared spectroscopy.

    As a result, Wang says, “Our finding highlights the critical role that interfacial electrolytes, in particular the intermolecular hydrogen bonding, can play in enhancing the activity of the electro-catalytic process. It also provides fundamental insights into proton transfer mechanisms at a quantum mechanical level, which can push the frontiers of knowing how protons and electrons interact at catalytic interfaces.”

    “The work is also exciting because it gives people a design principle for how they can tune the catalysts,” says Zhang. “We need some species right at a ‘sweet spot’ — not too active or too inert — to enhance the reaction rate.”

    With some of these techniques, says Reshma Rao, a recent doctoral graduate from MIT and now a postdoc at Imperial College, London, who is also a co-author of the paper, “we see up to a five-times increase in activity. I think the most exciting part of this research is the way it opens up a whole new dimension in the way we think about catalysis.” The field had hit “a kind of roadblock,” she says, in finding ways to design better materials. By focusing on the liquid layer rather than the surface of the material, “that’s kind of a whole different way of looking at this problem, and opens up a whole new dimension, a whole new axis along which we can change things and optimize some of these reaction rates.”

    The team also included Botao Huang, Bin Cai, and Livia Giordano in the MIT’s Research Laboratory of Electronics, and Shi-Gang Sun at Xiamen University in China. The work was supported by the Toyota Research Institute, and used the National Science Foundation’s Extreme Science and Engineering Environment. More