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      in Energy

      In nanotube science, is boron nitride the new carbon?

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      Engineers at MIT and the University of Tokyo have produced centimeter-scale structures, large enough for the eye to see, that are packed with hundreds of billions of hollow aligned fibers, or nanotubes, made from hexagonal boron nitride.

      Hexagonal boron nitride, or hBN, is a single-atom-thin material that has been coined “white graphene” for its transparent appearance and its similarity to carbon-based graphene in molecular structure and strength. It can also withstand higher temperatures than graphene, and is electrically insulating, rather than conductive. When hBN is rolled into nanometer-scale tubes, or nanotubes, its exceptional properties are significantly enhanced.

      The team’s results, published today in the journal ACS Nano, provide a route toward fabricating aligned boron nitride nanotubes (A-BNNTs) in bulk. The researchers plan to harness the technique to fabricate bulk-scale arrays of these nanotubes, which can then be combined with other materials to make stronger, more heat-resistant composites, for instance to shield space structures and hypersonic aircraft.

      As hBN is transparent and electrically insulating, the team also envisions incorporating the BNNTs into transparent windows and using them to electrically insulate sensors within electronic devices. The team is also investigating ways to weave the nanofibers into membranes for water filtration and for “blue energy” — a concept for renewable energy in which electricity is produced from the ionic filtering of salt water into fresh water.

      Brian Wardle, professor of aeronautics and astronautics at MIT, likens the team’s results to scientists’ decades-long, ongoing pursuit of manufacturing bulk-scale carbon nanotubes.

      “In 1991, a single carbon nanotube was identified as an interesting thing, but it’s been 30 years getting to bulk aligned carbon nanotubes, and the world’s not even fully there yet,” Wardle says. “With the work we’re doing, we’ve just short-circuited about 20 years in getting to bulk-scale versions of aligned boron nitride nanotubes.”

      Wardle is the senior author of the new study, which includes lead author and MIT research scientist Luiz Acauan, former MIT postdoc Haozhe Wang, and collaborators at the University of Tokyo.

      A vision, aligned

      Like graphene, hexagonal boron nitride has a molecular structure resembling chicken wire. In graphene, this chicken wire configuration is made entirely of carbon atoms, arranged in a repeating pattern of hexagons. For hBN, the hexagons are composed of alternating atoms of boron and nitrogen. In recent years, researchers have found that two-dimensional sheets of hBN exhibit exceptional properties of strength, stiffness, and resilience at high temperatures. When sheets of hBN are rolled into nanotube form, these properties are further enhanced, particularly when the nanotubes are aligned, like tiny trees in a densely packed forest.

      But finding ways to synthesize stable, high quality BNNTs has proven challenging. A handful of efforts to do so have produced low-quality, nonaligned fibers.

      “If you can align them, you have much better chance of harnessing BNNTs properties at the bulk scale to make actual physical devices, composites, and membranes,” Wardle says.

      In 2020, Rong Xiang and colleagues at the University of Tokyo found they could produce high-quality boron nitride nanotubes by first using a conventional approach of chemical vapor deposition to grow a forest of short, few micron-long carbon nanotubes. They then coated the carbon-based forest with “precursors” of boron and nitrogen gas, which when baked in an oven at high temperatures crystallized onto the carbon nanotubes to form high-quality nanotubes of hexagonal boron nitride with carbon nanotubes inside.

      Burning scaffolds

      In the new study, Wardle and Acauan have extend and scale Xiang’s approach, essentially removing the underlying carbon nanotubes and leaving the long boron nitride nanotubes to stand on their own. The team drew on the expertise of Wardle’s group, which has focused for years on fabricating high-quality aligned arrays of carbon nanotubes. With their current work, the researchers looked for ways to tweak the temperatures and pressures of the chemical vapor deposition process in order to remove the carbon nanotubes while leaving the boron nitride nanotubes intact.

      “The first few times we did it, it was completely ugly garbage,” Wardle recalls. “The tubes curled up into a ball, and they didn’t work.”

      Eventually, the team hit on a combination of temperatures, pressures, and precursors that did the trick. With this combination of processes, the researchers first reproduced the steps that Xiang took to synthesize the boron-nitride-coated carbon nanotubes. As hBN is resistant to higher temperatures than graphene, the team then cranked up the heat to burn away the underlying black carbon nanotube scaffold, while leaving the transparent, freestanding boron nitride nanotubes intact.
      By using carbon nanotubes as a scaffold, MIT engineers grow forests of “white graphene” that emerge (in MIT pattern) after burning away the black carbon scaffold. Courtesy of the researchersIn microscopic images, the team observed clear crystalline structures — evidence that the boron nitride nanotubes have a high quality. The structures were also dense: Within a square centimeter, the researchers were able to synthesize a forest of more than 100 billion aligned boron nitride nanotubes, that measured about a millimeter in height — large enough to be visible by eye. By nanotube engineering standards, these dimensions are considered to be “bulk” in scale.

      “We are now able to make these nanoscale fibers at bulk scale, which has never been shown before,” Acauan says.

      To demonstrate the flexibility of their technique, the team synthesized larger carbon-based structures, including a weave of carbon fibers, a mat of “fuzzy” carbon nanotubes, and sheets of randomly oriented carbon nanotubes known as “buckypaper.” They coated each carbon-based sample with boron and nitrogen precursors, then went through their process to burn away the underlying carbon. In each demonstration, they were left with a boron-nitride replica of the original black carbon scaffold.

      They also were able to “knock down” the forests of BNNTs, producing horizontally aligned fiber films that are a preferred configuration for incorporating into composite materials.

      “We are now working toward fibers to reinforce ceramic matrix composites, for hypersonic and space applications where there are very high temperatures, and for windows for devices that need to be optically transparent,” Wardle says. “You could make transparent materials that are reinforced with these very strong nanotubes.”

      This research was supported, in part, by Airbus, ANSYS, Boeing, Embraer, Lockheed Martin, Saab AB, and Teijin Carbon America through MIT’s Nano-Engineered Composite aerospace STructures (NECST) Consortium. More

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      in Energy

      Simplifying the production of lithium-ion batteries

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      When it comes to battery innovations, much attention gets paid to potential new chemistries and materials. Often overlooked is the importance of production processes for bringing down costs.

      Now the MIT spinout 24M Technologies has simplified lithium-ion battery production with a new design that requires fewer materials and fewer steps to manufacture each cell. The company says the design, which it calls “SemiSolid” for its use of gooey electrodes, reduces production costs by up to 40 percent. The approach also improves the batteries’ energy density, safety, and recyclability.

      Judging by industry interest, 24M is onto something. Since coming out of stealth mode in 2015, 24M has licensed its technology to multinational companies including Volkswagen, Fujifilm, Lucas TVS, Axxiva, and Freyr. Those last three companies are planning to build gigafactories (factories with gigawatt-scale annual production capacity) based on 24M’s technology in India, China, Norway, and the United States.

      “The SemiSolid platform has been proven at the scale of hundreds of megawatts being produced for residential energy-storage systems. Now we want to prove it at the gigawatt scale,” says 24M CEO Naoki Ota, whose team includes 24M co-founder, chief scientist, and MIT Professor Yet-Ming Chiang.

      Establishing large-scale production lines is only the first phase of 24M’s plan. Another key draw of its battery design is that it can work with different combinations of lithium-ion chemistries. That means 24M’s partners can incorporate better-performing materials down the line without substantially changing manufacturing processes.

      The kind of quick, large-scale production of next-generation batteries that 24M hopes to enable could have a dramatic impact on battery adoption across society — from the cost and performance of electric cars to the ability of renewable energy to replace fossil fuels.

      “This is a platform technology,” Ota says. “We’re not just a low-cost and high-reliability operator. That’s what we are today, but we can also be competitive with next-generation chemistry. We can use any chemistry in the market without customers changing their supply chains. Other startups are trying to address that issue tomorrow, not today. Our tech can address the issue today and tomorrow.”

      A simplified design

      Chiang, who is MIT’s Kyocera Professor of Materials Science and Engineering, got his first glimpse into large-scale battery production after co-founding another battery company, A123 Systems, in 2001. As that company was preparing to go public in the late 2000s, Chiang began wondering if he could design a battery that would be easier to manufacture.

      “I got this window into what battery manufacturing looked like, and what struck me was that even though we pulled it off, it was an incredibly complicated manufacturing process,” Chiang says. “It derived from magnetic tape manufacturing that was adapted to batteries in the late 1980s.”

      In his lab at MIT, where he’s been a professor since 1985, Chiang started from scratch with a new kind of device he called a “semi-solid flow battery” that pumps liquids carrying particle-based electrodes to and from tanks to store a charge.

      In 2010, Chiang partnered with W. Craig Carter, who is MIT’s POSCO Professor of Materials Science and Engineering, and the two professors supervised a student, Mihai Duduta ’11, who explored flow batteries for his undergraduate thesis. Within a month, Duduta had developed a prototype in Chiang’s lab, and 24M was born. (Duduta was the company’s first hire.)

      But even as 24M worked with MIT’s Technology Licensing Office (TLO) to commercialize research done in Chiang’s lab, people in the company including Duduta began rethinking the flow battery concept. An internal cost analysis by Carter, who consulted for 24M for several years, ultimately lead the researchers to change directions.

      That left the company with loads of the gooey slurry that made up the electrodes in their flow batteries. A few weeks after Carter’s cost analysis, Duduta, then a senior research scientist at 24M, decided to start using the slurry to assemble batteries by hand, mixing the gooey electrodes directly into the electrolyte. The idea caught on.

      The main components of batteries are the positive and negatively charged electrodes and the electrolyte material that allows ions to flow between them. Traditional lithium-ion batteries use solid electrodes separated from the electrolyte by layers of inert plastics and metals, which hold the electrodes in place.

      Stripping away the inert materials of traditional batteries and embracing the gooey electrode mix gives 24M’s design a number of advantages.

      For one, it eliminates the energy-intensive process of drying and solidifying the electrodes in traditional lithium-ion production. The company says it also reduces the need for more than 80 percent of the inactive materials in traditional batteries, including expensive ones like copper and aluminum. The design also requires no binder and features extra thick electrodes, improving the energy density of the batteries.

      “When you start a company, the smart thing to do is to revisit all of your assumptions  and ask what is the best way to accomplish your objectives, which in our case was simply-manufactured, low-cost batteries,” Chiang says. “We decided our real value was in making a lithium-ion suspension that was electrochemically active from the beginning, with electrolyte in it, and you just use the electrolyte as the processing solvent.”

      In 2017, 24M participated in the MIT Industrial Liaison Program’s STEX25 Startup Accelerator, in which Chiang and collaborators made critical industry connections that would help it secure early partnerships. 24M has also collaborated with MIT researchers on projects funded by the Department of Energy.

      Enabling the battery revolution

      Most of 24M’s partners are eyeing the rapidly growing electric vehicle (EV) market for their batteries, and the founders believe their technology will accelerate EV adoption. (Battery costs make up 30 to 40 percent of the price of EVs, according to the Institute for Energy Research).

      “Lithium-ion batteries have made huge improvements over the years, but even Elon Musk says we need some breakthrough technology,” Ota says, referring to the CEO of EV firm Tesla. “To make EVs more common, we need a production cost breakthrough; we can’t just rely on cost reduction through scaling because we already make a lot of batteries today.”

      24M is also working to prove out new battery chemistries that its partners could quickly incorporate into their gigafactories. In January of this year, 24M received a grant from the Department of Energy’s ARPA-E program to develop and scale a high-energy-density battery that uses a lithium metal anode and semi-solid cathode for use in electric aviation.

      That project is one of many around the world designed to validate new lithium-ion battery chemistries that could enable a long-sought battery revolution. As 24M continues to foster the creation of large scale, global production lines, the team believes it is well-positioned to turn lab innovations into ubiquitous, world-changing products.

      “This technology is a platform, and our vision is to be like Google’s Android [operating system], where other people can build things on our platform,” Ota says. “We want to do that but with hardware. That’s why we’re licensing the technology. Our partners can use the same production lines to get the benefits of new chemistries and approaches. This platform gives everyone more options.” More

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      in Energy

      Ocean scientists measure sediment plume stirred up by deep-sea-mining vehicle

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      What will be the impact to the ocean if humans are to mine the deep sea? It’s a question that’s gaining urgency as interest in marine minerals has grown.

      The ocean’s deep-sea bed is scattered with ancient, potato-sized rocks called “polymetallic nodules” that contain nickel and cobalt — minerals that are in high demand for the manufacturing of batteries, such as for powering electric vehicles and storing renewable energy, and in response to factors such as increasing urbanization. The deep ocean contains vast quantities of mineral-laden nodules, but the impact of mining the ocean floor is both unknown and highly contested.

      Now MIT ocean scientists have shed some light on the topic, with a new study on the cloud of sediment that a collector vehicle would stir up as it picks up nodules from the seafloor.

      The study, appearing today in Science Advances, reports the results of a 2021 research cruise to a region of the Pacific Ocean known as the Clarion Clipperton Zone (CCZ), where polymetallic nodules abound. There, researchers equipped a pre-prototype collector vehicle with instruments to monitor sediment plume disturbances as the vehicle maneuvered across the seafloor, 4,500 meters below the ocean’s surface. Through a sequence of carefully conceived maneuvers. the MIT scientists used the vehicle to monitor its own sediment cloud and measure its properties.

      Their measurements showed that the vehicle created a dense plume of sediment in its wake, which spread under its own weight, in a phenomenon known in fluid dynamics as a “turbidity current.” As it gradually dispersed, the plume remained relatively low, staying within 2 meters of the seafloor, as opposed to immediately lofting higher into the water column as had been postulated.

      “It’s quite a different picture of what these plumes look like, compared to some of the conjecture,” says study co-author Thomas Peacock, professor of mechanical engineering at MIT. “Modeling efforts of deep-sea mining plumes will have to account for these processes that we identified, in order to assess their extent.”

      The study’s co-authors include lead author Carlos Muñoz-Royo, Raphael Ouillon, and Souha El Mousadik of MIT; and Matthew Alford of the Scripps Institution of Oceanography.

      Deep-sea maneuvers

      To collect polymetallic nodules, some mining companies are proposing to deploy tractor-sized vehicles to the bottom of the ocean. The vehicles would vacuum up the nodules along with some sediment along their path. The nodules and sediment would then be separated inside of the vehicle, with the nodules sent up through a riser pipe to a surface vessel, while most of the sediment would be discharged immediately behind the vehicle.

      Peacock and his group have previously studied the dynamics of the sediment plume that associated surface operation vessels may pump back into the ocean. In their current study, they focused on the opposite end of the operation, to measure the sediment cloud created by the collectors themselves.

      In April 2021, the team joined an expedition led by Global Sea Mineral Resources NV (GSR), a Belgian marine engineering contractor that is exploring the CCZ for ways to extract metal-rich nodules. A European-based science team, Mining Impacts 2, also conducted separate studies in parallel. The cruise was the first in over 40 years to test a “pre-prototype” collector vehicle in the CCZ. The machine, called Patania II, stands about 3 meters high, spans 4 meters wide, and is about one-third the size of what a commercial-scale vehicle is expected to be.

      While the contractor tested the vehicle’s nodule-collecting performance, the MIT scientists monitored the sediment cloud created in the vehicle’s wake. They did so using two maneuvers that the vehicle was programmed to take: a “selfie,” and a “drive-by.”

      Both maneuvers began in the same way, with the vehicle setting out in a straight line, all its suction systems turned on. The researchers let the vehicle drive along for 100 meters, collecting any nodules in its path. Then, in the “selfie” maneuver, they directed the vehicle to turn off its suction systems and double back around to drive through the cloud of sediment it had just created. The vehicle’s installed sensors measured the concentration of sediment during this “selfie” maneuver, allowing the scientists to monitor the cloud within minutes of the vehicle stirring it up.

      Play video

      A movie of the Patania II pre-prototype collector vehicle entering, driving through, and leaving the low-lying turbidity current plume as part of a selfie operation. For scale, the instrumentation post attached to the front of the vehicle reaches about 3m above the seabed. The movie is sped up by a factor of 20. Credit: Global Sea Mineral Resources

      For the “drive-by” maneuver, the researchers placed a sensor-laden mooring 50 to 100 meters from the vehicle’s planned tracks. As the vehicle drove along collecting nodules, it created a plume that eventually spread past the mooring after an hour or two. This “drive-by” maneuver enabled the team to monitor the sediment cloud over a longer timescale of several hours, capturing the plume evolution.

      Out of steam

      Over multiple vehicle runs, Peacock and his team were able to measure and track the evolution of the sediment plume created by the deep-sea-mining vehicle.

      “We saw that the vehicle would be driving in clear water, seeing the nodules on the seabed,” Peacock says. “And then suddenly there’s this very sharp sediment cloud coming through when the vehicle enters the plume.”

      From the selfie views, the team observed a behavior that was predicted by some of their previous modeling studies: The vehicle stirred up a heavy amount of sediment that was dense enough that, even after some mixing with the surrounding water, it generated a plume that behaved almost as a separate fluid, spreading under its own weight in what’s known as a turbidity current.

      “The turbidity current spreads under its own weight for some time, tens of minutes, but as it does so, it’s depositing sediment on the seabed and eventually running out of steam,” Peacock says. “After that, the ocean currents get stronger than the natural spreading, and the sediment transitions to being carried by the ocean currents.”

      By the time the sediment drifted past the mooring, the researchers estimate that 92 to 98 percent of the sediment either settled back down or remained within 2 meters of the seafloor as a low-lying cloud. There is, however, no guarantee that the sediment always stays there rather than drifting further up in the water column. Recent and future studies by the research team are looking into this question, with the goal of consolidating understanding for deep-sea mining sediment plumes.

      “Our study clarifies the reality of what the initial sediment disturbance looks like when you have a certain type of nodule mining operation,” Peacock says. “The big takeaway is that there are complex processes like turbidity currents that take place when you do this kind of collection. So, any effort to model a deep-sea-mining operation’s impact will have to capture these processes.”

      “Sediment plumes produced by deep-seabed mining are a major concern with regards to environmental impact, as they will spread over potentially large areas beyond the actual site of mining and affect deep-sea life,” says Henko de Stigter, a marine geologist at the Royal Netherlands Institute for Sea Research, who was not involved in the research. “The current paper provides essential insight in the initial development of these plumes.”

      This research was supported, in part, by the National Science Foundation, ARPA-E, the 11th Hour Project, the Benioff Ocean Initiative, and Global Sea Mineral Resources. The funders had no role in any aspects of the research analysis, the research team states. More

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      in Energy

      A lasting — and valuable — legacy

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      Betar Gallant, MIT associate professor and Class of 1922 Career Development Chair in Mechanical Engineering, grew up in a curious, independently minded family. Her mother had multiple jobs over the years, including in urban planning and in the geospatial field. Her father, although formally trained in English, read textbooks of all kinds from cover to cover, taught himself numerous technical fields including engineering, and worked successfully in them. When Gallant was very young, she and her father did science experiments in the basement.

      It wasn’t until she was in her teenage years, though, that she says she got drawn into science. Her father, who had fallen ill five years before, died when Gallant was 16, and while grieving, “when I was missing him the most,” she started to look at what had captivated her father.

      “I started to take a deeper interest in the things he had spent his life working on as a way to feel closer to him in his absence,” Gallant says. “I spent a few long months one summer looking through some of the things he had worked on, and found myself reading physics textbooks. That was enough, and I was hooked.”

      The love for independently finding and understanding solutions, that she had apparently inherited from her parents, eventually took her to the professional love of her life: electrochemistry.

      As an undergraduate at MIT, Gallant did an Undergraduate Research Opportunities Program project with Professor Yang Shao-Horn’s research group that went from her sophomore year through her senior thesis. This was Gallant’s first official exposure to electrochemistry.

      “When I met Yang, she showed me very quickly how challenging and enriching electrochemistry can be, and there was real conviction and excitement in how she and her group members talked about research,” Gallant says. “It was totally eye-opening, and I’m fortunate that she was a (relatively rare) electrochemist in a mechanical engineering department, or else I likely would not have been able to go down that road.”

      Play video

      Gallant earned three degrees at MIT (’08, SM ’10, and PhD ’13). Before joining the MIT faculty in 2016, she was a Kavli Nanoscience Institute Prize Postdoctoral Fellow at Caltech in the Division of Chemistry and Chemical Engineering.

      Her passion for electrochemistry is enormous. “Electrons are just dazzling — they power so much of our everyday world, and are the key to a renewable future,” she says, explaining that despite electrons’ amazing potential, isolated electrons cannot be stored and produced on demand, because “nature doesn’t allow excessive amounts of charge imbalances to accumulate.”

      Electrons can, however, be stored on molecules, in bonds and in metal ions or nonmetal centers that are able to lose and gain electrons — as long as positive charge transfers occur to accommodate the electrons.

      “Here’s where chemistry rears its head,” Gallant says. “What types of molecules or materials can behave in this way? How do we store as much charge as possible while making the weight and volume as low as possible?”

      Gallant points out that early battery developers using lithium and ions built a technology that “has arguably shaped our modern world more than any other.

      “If you look at some early papers, the concepts of how a lithium-ion battery or a lithium metal anode worked were sketched out by hand — they had been deduced to be true, before the field even had the tools to prove all the mechanisms were actually occurring — yet even now, those ideas are still turning out to be right!”

      Gallant says, “that’s because if you truly understand the basic principles of electrochemistry, you can start to intuit how systems will behave. Once you can do that, you can really begin to engineer better materials and devices.”

      Truly her father’s daughter, Gallant’s emphasis is on independently finding solutions.

      “Ultimately, it’s a race to have the best mental models,” she says. “A great lab and lots of funding and personnel to run it are very nice, but the most valuable tools in the toolbox are solid mental models and a way of thinking about electrochemistry, which is actually very personalized depending on the researcher.”

      She says one project with immediate impact that’s coming out of her Gallant Energy and Carbon Conversion Lab relates to primary (non-rechargeable) battery work that she and her team are working to commercialize. It involves injecting new electrochemically active electrolytes into leading high-energy batteries as they’re being assembled. Replacing a conventional electrolyte with the new chemistry decreases the normally inactive weight of the battery and boosts the energy substantially, Gallant says. One important application of such batteries would be for medical devices such as pacemakers.

      “If you can extend lifetime, you’re talking about longer times between invasive replacement surgeries, which really affects patient quality of life,” she says.

      Gallant’s team is also leading efforts to enable higher-energy rechargeable lithium-ion batteries for electric vehicles. Key to a step-change in energy, and therefore driving range, is to use a lithium metal anode in place of graphite. Lithium metal is highly reactive, however, with all battery electrolytes, and its interface needs to be stabilized in ways that still elude researchers. Gallant’s team is developing design guidelines for such interfaces, and for next-generation electrolytes to form and sustain these interfaces. Gallant says that applying the technology to that purpose and commercializing it would be “a bit longer-term, but I believe this change to lithium anodes will happen, and it’s just a matter of when.”

      About six years ago, when Gallant founded her lab, she and her team started introducing carbon dioxide into batteries as a way to experiment with electrochemical conversion of the greenhouse gas. She says they realized that batteries do not present the best practical technology to mitigate CO2, but their experimentation did open up new paths to carbon capture and conversion. “That work allowed us to think creatively, and we started to realize that there is tremendous potential to manipulate CO2 reactions by carefully designing the electrochemical environment.” That led her team to the idea of conducting electrochemical transformations on CO2 from a captured state bound to a capture sorbent, replacing the energy-intense regeneration step of today’s capture processes and streamlining the process.  

      “Now we’re seeing other researchers working on that, too, and taking this idea in exciting directions — it’s a very challenging and very rich topic,” she says.

      Gallant has won awards including an MIT Bose Fellowship, the Army Research Office Young Investigator Award, the Scialog Fellowship in Energy Storage and in Negative Emissions Science, a CAREER award from the National Science Foundation, the Ruth and Joel Spira Award for Distinguished Teaching at MIT, the Electrochemical Society (ECS) Battery Division Early Career award, and an ECS-Toyota Young Investigator Award.

      These days, Gallant does some of her best thinking while brainstorming with her research group members and with her husband, who is also an academic. She says being a professor at MIT means she has “a queue of things to think about,” but she sometimes gets awarded with a revelation.

      “My brain gets overloaded because I can’t think through everything instantaneously; ideas have to get in line! So there’s a lot going on in the background at all times,” she say. “I don’t know how it works, but sometimes I’ll be going for a walk or doing something else, and an idea breaks through. Those are the fun ones.” More

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      in Energy

      A simple way to significantly increase lifetimes of fuel cells and other devices

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      In research that could jump-start work on a range of technologies including fuel cells, which are key to storing solar and wind energy, MIT researchers have found a relatively simple way to increase the lifetimes of these devices: changing the pH of the system.

      Fuel and electrolysis cells made of materials known as solid metal oxides are of interest for several reasons. For example, in the electrolysis mode, they are very efficient at converting electricity from a renewable source into a storable fuel like hydrogen or methane that can be used in the fuel cell mode to generate electricity when the sun isn’t shining or the wind isn’t blowing. They can also be made without using costly metals like platinum. However, their commercial viability has been hampered, in part, because they degrade over time. Metal atoms seeping from the interconnects used to construct banks of fuel/electrolysis cells slowly poison the devices.

      “What we’ve been able to demonstrate is that we can not only reverse that degradation, but actually enhance the performance above the initial value by controlling the acidity of the air-electrode interface,” says Harry L. Tuller, the R.P. Simmons Professor of Ceramics and Electronic Materials in MIT’s Department of Materials Science and Engineering (DMSE).

      The research, initially funded by the U.S. Department of Energy through the Office of Fossil Energy and Carbon Management’s (FECM) National Energy Technology Laboratory, should help the department meet its goal of significantly cutting the degradation rate of solid oxide fuel cells by 2035 to 2050.

      “Extending the lifetime of solid oxide fuels cells helps deliver the low-cost, high-efficiency hydrogen production and power generation needed for a clean energy future,” says Robert Schrecengost, acting director of FECM’s Division of Hydrogen with Carbon Management. “The department applauds these advancements to mature and ultimately commercialize these technologies so that we can provide clean and reliable energy for the American people.”

      “I’ve been working in this area my whole professional life, and what I’ve seen until now is mostly incremental improvements,” says Tuller, who was recently named a 2022 Materials Research Society Fellow for his career-long work in solid-state chemistry and electrochemistry. “People are normally satisfied with seeing improvements by factors of tens-of-percent. So, actually seeing much larger improvements and, as importantly, identifying the source of the problem and the means to work around it, issues that we’ve been struggling with for all these decades, is remarkable.”

      Says James M. LeBeau, the John Chipman Associate Professor of Materials Science and Engineering at MIT, who was also involved in the research, “This work is important because it could overcome [some] of the limitations that have prevented the widespread use of solid oxide fuel cells. Additionally, the basic concept can be applied to many other materials used for applications in the energy-related field.”

      A report describing the work was reported Aug. 11, in Energy & Environmental Science. Additional authors of the paper are Han Gil Seo, a DMSE postdoc; Anna Staerz, formerly a DMSE postdoc, now at Interuniversity Microelectronics Centre (IMEC) Belgium and soon to join the Colorado School of Mines faculty; Dennis S. Kim, a DMSE postdoc; Dino Klotz, a DMSE visiting scientist, now at Zurich Instruments; Michael Xu, a DMSE graduate student; and Clement Nicollet, formerly a DMSE postdoc, now at the Université de Nantes. Seo and Staerz contributed equally to the work.

      Changing the acidity

      A fuel/electrolysis cell has three principal parts: two electrodes (a cathode and anode) separated by an electrolyte. In the electrolysis mode, electricity from, say, the wind, can be used to generate storable fuel like methane or hydrogen. On the other hand, in the reverse fuel cell reaction, that storable fuel can be used to create electricity when the wind isn’t blowing.

      A working fuel/electrolysis cell is composed of many individual cells that are stacked together and connected by steel metal interconnects that include the element chrome to keep the metal from oxidizing. But “it turns out that at the high temperatures that these cells run, some of that chrome evaporates and migrates to the interface between the cathode and the electrolyte, poisoning the oxygen incorporation reaction,” Tuller says. After a certain point, the efficiency of the cell has dropped to a point where it is not worth operating any longer.

      “So if you can extend the life of the fuel/electrolysis cell by slowing down this process, or ideally reversing it, you could go a long way towards making it practical,” Tuller says.

      The team showed that you can do both by controlling the acidity of the cathode surface. They also explained what is happening.

      To achieve their results, the team coated the fuel/electrolysis cell cathode with lithium oxide, a compound that changes the relative acidity of the surface from being acidic to being more basic. “After adding a small amount of lithium, we were able to recover the initial performance of a poisoned cell,” Tuller says. When the engineers added even more lithium, the performance improved far beyond the initial value. “We saw improvements of three to four orders of magnitude in the key oxygen reduction reaction rate and attribute the change to populating the surface of the electrode with electrons needed to drive the oxygen incorporation reaction.”

      The engineers went on to explain what is happening by observing the material at the nanoscale, or billionths of a meter, with state-of-the-art transmission electron microscopy and electron energy loss spectroscopy at MIT.nano. “We were interested in understanding the distribution of the different chemical additives [chromium and lithium oxide] on the surface,” says LeBeau.

      They found that the lithium oxide effectively dissolves the chromium to form a glassy material that no longer serves to degrade the cathode performance.

      Applications for sensors, catalysts, and more

      Many technologies like fuel cells are based on the ability of the oxide solids to rapidly breathe oxygen in and out of their crystalline structures, Tuller says. The MIT work essentially shows how to recover — and speed up — that ability by changing the surface acidity. As a result, the engineers are optimistic that the work could be applied to other technologies including, for example, sensors, catalysts, and oxygen permeation-based reactors.

      The team is also exploring the effect of acidity on systems poisoned by different elements, like silica.

      Concludes Tuller: “As is often the case in science, you stumble across something and notice an important trend that was not appreciated previously. Then you test that concept further, and you discover that it is really very fundamental.”

      In addition to the DOE, this work was also funded by the National Research Foundation of Korea, the MIT Department of Materials Science and Engineering via Tuller’s appointment as the R.P. Simmons Professor of Ceramics and Electronic Materials, and the U.S. Air Force Office of Scientific Research. More

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      A new concept for low-cost batteries

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      As the world builds out ever larger installations of wind and solar power systems, the need is growing fast for economical, large-scale backup systems to provide power when the sun is down and the air is calm. Today’s lithium-ion batteries are still too expensive for most such applications, and other options such as pumped hydro require specific topography that’s not always available.

      Now, researchers at MIT and elsewhere have developed a new kind of battery, made entirely from abundant and inexpensive materials, that could help to fill that gap.

      The new battery architecture, which uses aluminum and sulfur as its two electrode materials, with a molten salt electrolyte in between, is described today in the journal Nature, in a paper by MIT Professor Donald Sadoway, along with 15 others at MIT and in China, Canada, Kentucky, and Tennessee.

      “I wanted to invent something that was better, much better, than lithium-ion batteries for small-scale stationary storage, and ultimately for automotive [uses],” explains Sadoway, who is the John F. Elliott Professor Emeritus of Materials Chemistry.

      In addition to being expensive, lithium-ion batteries contain a flammable electrolyte, making them less than ideal for transportation. So, Sadoway started studying the periodic table, looking for cheap, Earth-abundant metals that might be able to substitute for lithium. The commercially dominant metal, iron, doesn’t have the right electrochemical properties for an efficient battery, he says. But the second-most-abundant metal in the marketplace — and actually the most abundant metal on Earth — is aluminum. “So, I said, well, let’s just make that a bookend. It’s gonna be aluminum,” he says.

      Then came deciding what to pair the aluminum with for the other electrode, and what kind of electrolyte to put in between to carry ions back and forth during charging and discharging. The cheapest of all the non-metals is sulfur, so that became the second electrode material. As for the electrolyte, “we were not going to use the volatile, flammable organic liquids” that have sometimes led to dangerous fires in cars and other applications of lithium-ion batteries, Sadoway says. They tried some polymers but ended up looking at a variety of molten salts that have relatively low melting points — close to the boiling point of water, as opposed to nearly 1,000 degrees Fahrenheit for many salts. “Once you get down to near body temperature, it becomes practical” to make batteries that don’t require special insulation and anticorrosion measures, he says.

      The three ingredients they ended up with are cheap and readily available — aluminum, no different from the foil at the supermarket; sulfur, which is often a waste product from processes such as petroleum refining; and widely available salts. “The ingredients are cheap, and the thing is safe — it cannot burn,” Sadoway says.

      In their experiments, the team showed that the battery cells could endure hundreds of cycles at exceptionally high charging rates, with a projected cost per cell of about one-sixth that of comparable lithium-ion cells. They showed that the charging rate was highly dependent on the working temperature, with 110 degrees Celsius (230 degrees Fahrenheit) showing 25 times faster rates than 25 C (77 F).

      Surprisingly, the molten salt the team chose as an electrolyte simply because of its low melting point turned out to have a fortuitous advantage. One of the biggest problems in battery reliability is the formation of dendrites, which are narrow spikes of metal that build up on one electrode and eventually grow across to contact the other electrode, causing a short-circuit and hampering efficiency. But this particular salt, it happens, is very good at preventing that malfunction.

      The chloro-aluminate salt they chose “essentially retired these runaway dendrites, while also allowing for very rapid charging,” Sadoway says. “We did experiments at very high charging rates, charging in less than a minute, and we never lost cells due to dendrite shorting.”

      “It’s funny,” he says, because the whole focus was on finding a salt with the lowest melting point, but the catenated chloro-aluminates they ended up with turned out to be resistant to the shorting problem. “If we had started off with trying to prevent dendritic shorting, I’m not sure I would’ve known how to pursue that,” Sadoway says. “I guess it was serendipity for us.”

      What’s more, the battery requires no external heat source to maintain its operating temperature. The heat is naturally produced electrochemically by the charging and discharging of the battery. “As you charge, you generate heat, and that keeps the salt from freezing. And then, when you discharge, it also generates heat,” Sadoway says. In a typical installation used for load-leveling at a solar generation facility, for example, “you’d store electricity when the sun is shining, and then you’d draw electricity after dark, and you’d do this every day. And that charge-idle-discharge-idle is enough to generate enough heat to keep the thing at temperature.”

      This new battery formulation, he says, would be ideal for installations of about the size needed to power a single home or small to medium business, producing on the order of a few tens of kilowatt-hours of storage capacity.

      For larger installations, up to utility scale of tens to hundreds of megawatt hours, other technologies might be more effective, including the liquid metal batteries Sadoway and his students developed several years ago and which formed the basis for a spinoff company called Ambri, which hopes to deliver its first products within the next year. For that invention, Sadoway was recently awarded this year’s European Inventor Award.

      The smaller scale of the aluminum-sulfur batteries would also make them practical for uses such as electric vehicle charging stations, Sadoway says. He points out that when electric vehicles become common enough on the roads that several cars want to charge up at once, as happens today with gasoline fuel pumps, “if you try to do that with batteries and you want rapid charging, the amperages are just so high that we don’t have that amount of amperage in the line that feeds the facility.” So having a battery system such as this to store power and then release it quickly when needed could eliminate the need for installing expensive new power lines to serve these chargers.

      The new technology is already the basis for a new spinoff company called Avanti, which has licensed the patents to the system, co-founded by Sadoway and Luis Ortiz ’96 ScD ’00, who was also a co-founder of Ambri. “The first order of business for the company is to demonstrate that it works at scale,” Sadoway says, and then subject it to a series of stress tests, including running through hundreds of charging cycles.

      Would a battery based on sulfur run the risk of producing the foul odors associated with some forms of sulfur? Not a chance, Sadoway says. “The rotten-egg smell is in the gas, hydrogen sulfide. This is elemental sulfur, and it’s going to be enclosed inside the cells.” If you were to try to open up a lithium-ion cell in your kitchen, he says (and please don’t try this at home!), “the moisture in the air would react and you’d start generating all sorts of foul gases as well. These are legitimate questions, but the battery is sealed, it’s not an open vessel. So I wouldn’t be concerned about that.”

      The research team included members from Peking University, Yunnan University and the Wuhan University of Technology, in China; the University of Louisville, in Kentucky; the University of Waterloo, in Canada; Oak Ridge National Laboratory, in Tennessee; and MIT. The work was supported by the MIT Energy Initiative, the MIT Deshpande Center for Technological Innovation, and ENN Group. More

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      Building better batteries, faster

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      To help combat climate change, many car manufacturers are racing to add more electric vehicles in their lineups. But to convince prospective buyers, manufacturers need to improve how far these cars can go on a single charge. One of their main challenges? Figuring out how to make extremely powerful but lightweight batteries.

      Typically, however, it takes decades for scientists to thoroughly test new battery materials, says Pablo Leon, an MIT graduate student in materials science. To accelerate this process, Leon is developing a machine-learning tool for scientists to automate one of the most time-consuming, yet key, steps in evaluating battery materials.

      With his tool in hand, Leon plans to help search for new materials to enable the development of powerful and lightweight batteries. Such batteries would not only improve the range of EVs, but they could also unlock potential in other high-power systems, such as solar energy systems that continuously deliver power, even at night.

      From a young age, Leon knew he wanted to pursue a PhD, hoping to one day become a professor of engineering, like his father. Growing up in College Station, Texas, home to Texas A&M University, where his father worked, many of Leon’s friends also had parents who were professors or affiliated with the university. Meanwhile, his mom worked outside the university, as a family counselor in a neighboring city.

      In college, Leon followed in his father’s and older brother’s footsteps to become a mechanical engineer, earning his bachelor’s degree at Texas A&M. There, he learned how to model the behaviors of mechanical systems, such as a metal spring’s stiffness. But he wanted to delve deeper, down to the level of atoms, to understand exactly where these behaviors come from.

      So, when Leon applied to graduate school at MIT, he switched fields to materials science, hoping to satisfy his curiosity. But the transition to a different field was “a really hard process,” Leon says, as he rushed to catch up to his peers.

      To help with the transition, Leon sought out a congenial research advisor and found one in Rafael Gómez-Bombarelli, an assistant professor in the Department of Materials Science and Engineering (DMSE). “Because he’s from Spain and my parents are Peruvian, there’s a cultural ease with the way we talk,” Leon says. According to Gómez-Bombarelli, sometimes the two of them even discuss research in Spanish — a “rare treat.” That connection has empowered Leon to freely brainstorm ideas or talk through concerns with his advisor, enabling him to make significant progress in his research.

      Leveraging machine learning to research battery materials

      Scientists investigating new battery materials generally use computer simulations to understand how different combinations of materials perform. These simulations act as virtual microscopes for batteries, zooming in to see how materials interact at an atomic level. With these details, scientists can understand why certain combinations do better, guiding their search for high-performing materials.

      But building accurate computer simulations is extremely time-intensive, taking years and sometimes even decades. “You need to know how every atom interacts with every other atom in your system,” Leon says. To create a computer model of these interactions, scientists first make a rough guess at a model using complex quantum mechanics calculations. They then compare the model with results from real-life experiments, manually tweaking different parts of the model, including the distances between atoms and the strength of chemical bonds, until the simulation matches real life.

      With well-studied battery materials, the simulation process is somewhat easier. Scientists can buy simulation software that includes pre-made models, Leon says, but these models often have errors and still require additional tweaking.

      To build accurate computer models more quickly, Leon is developing a machine-learning-based tool that can efficiently guide the trial-and-error process. “The hope with our machine learning framework is to not have to rely on proprietary models or do any hand-tuning,” he says. Leon has verified that for well-studied materials, his tool is as accurate as the manual method for building models.

      With this system, scientists will have a single, standardized approach for building accurate models in lieu of the patchwork of approaches currently in place, Leon says.

      Leon’s tool comes at an opportune time, when many scientists are investigating a new paradigm of batteries: solid-state batteries. Compared to traditional batteries, which contain liquid electrolytes, solid-state batteries are safer, lighter, and easier to manufacture. But creating versions of these batteries that are powerful enough for EVs or renewable energy storage is challenging.

      This is largely because in battery chemistry, ions dislike flowing through solids and instead prefer liquids, in which atoms are spaced further apart. Still, scientists believe that with the right combination of materials, solid-state batteries can provide enough electricity for high-power systems, such as EVs. 

      Leon plans to use his machine-learning tool to help look for good solid-state battery materials more quickly. After he finds some powerful candidates in simulations, he’ll work with other scientists to test out the new materials in real-world experiments.

      Helping students navigate graduate school

      To get to where he is today, doing exciting and impactful research, Leon credits his community of family and mentors. Because of his upbringing, Leon knew early on which steps he would need to take to get into graduate school and work toward becoming a professor. And he appreciates the privilege of his position, even more so as a Peruvian American, given that many Latino students are less likely to have access to the same resources. “I understand the academic pipeline in a way that I think a lot of minority groups in academia don’t,” he says.

      Now, Leon is helping prospective graduate students from underrepresented backgrounds navigate the pipeline through the DMSE Application Assistance Program. Each fall, he mentors applicants for the DMSE PhD program at MIT, providing feedback on their applications and resumes. The assistance program is student-run and separate from the admissions process.

      Knowing firsthand how invaluable mentorship is from his relationship with his advisor, Leon is also heavily involved in mentoring junior PhD students in his department. This past year, he served as the academic chair on his department’s graduate student organization, the Graduate Materials Council. With MIT still experiencing disruptions from Covid-19, Leon noticed a problem with student cohesiveness. “I realized that traditional [informal] modes of communication across [incoming class] years had been cut off,” he says, making it harder for junior students to get advice from their senior peers. “They didn’t have any community to fall back on.”

      To help fix this problem, Leon served as a go-to mentor for many junior students. He helped second-year PhD students prepare for their doctoral qualification exam, an often-stressful rite of passage. He also hosted seminars for first-year students to teach them how to make the most of their classes and help them acclimate to the department’s fast-paced classes. For fun, Leon organized an axe-throwing event to further facilitate student cameraderie.

      Leon’s efforts were met with success. Now, “newer students are building back the community,” he says, “so I feel like I can take a step back” from being academic chair. He will instead continue mentoring junior students through other programs within the department. He also plans to extend his community-building efforts among faculty and students, facilitating opportunities for students to find good mentors and work on impactful research. With these efforts, Leon hopes to help others along the academic pipeline that he’s become familiar with, journeying together over their PhDs. More

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      Donald Sadoway wins European Inventor Award for liquid metal batteries

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      MIT Professor Donald Sadoway has won the 2022 European Inventor Award, in the category for Non-European Patent Office Countries, for his work on liquid metal batteries that could enable the long-term storage of renewable energy.

      Sadoway is the John F. Elliott Professor of Materials Chemistry in MIT’s Department of Materials Science and Engineering, and a longtime supporter and friend of the Materials Research Laboratory.

      “By enabling the large-scale storage of renewable energy, Donald Sadoway’s invention is a huge step towards the deployment of carbon-free electricity generation,” says António Campinos, president of the European Patent Office. “He has spent his career studying electrochemistry and has transformed this expertise into an invention that represents a huge step forward in the transition to green energy.”

      Sadoway was honored at the 2022 European Inventor Award ceremony on June 21. The award is one of Europe’s most prestigious innovation prizes and is presented annually to outstanding inventors from Europe and beyond who have made an exceptional contribution to society, technological progress, and economic growth.

      When accepting the award in Munich, Sadoway told the audience:

      “I am astonished. When I look at all the patented technologies that are represented at this event I see an abundance of excellence, all of them solutions to pressing problems. I wonder if the judges are assessing not only degrees of excellence but degrees of urgency. The liquid metal battery addresses an existential threat to the health of our atmosphere which is related to climate change.

      “By hosting this event the EPO celebrates invention. The thread that connects all the inventors is their efforts to make the world a better place. In my judgment there is no nobler pursuit. So perhaps this is a celebration of nobility.”

      Sadoway’s liquid metal batteries consist of three liquid layers of different densities, which naturally separate in the same way as oil and vinegar do in a salad dressing. The top and bottom layers are made from molten metals, with a middle layer of molten liquid salt.

      To keep the metals liquid, the batteries need to operate at extremely high temperatures, so Sadoway designed a system that is self-heating and insulated, requiring no external heating or cooling. They have a lifespan of more than 20 years, can maintain 99 percent of their capacity over 5,000 charging cycles, and have no combustible materials, meaning there is no fire risk.

      In 2010, with a patent for his invention and support from Bill Gates, Sadoway co-founded Ambri, based in Marlborough, Massachusetts just outside Boston, to develop a commercial product. The company will soon install a unit on a 3,700-acre development for a data center in Nevada. This battery will store energy from a reported 500 megawatts of on-site renewable generation, the same output as a natural gas power plant.

      Born in 1950 into a family of Ukrainian immigrants in Canada, Sadoway studied chemical metallurgy specializing in what he calls “extreme electrochemistry” — chemical reactions in molten salts and liquid metals that have been heated to over 500 degrees Celsius. After earning his BASc, MASc, and PhD, all from the University of Toronto, he joined the faculty at MIT in 1978. More