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    Designing better batteries for electric vehicles

    The urgent need to cut carbon emissions is prompting a rapid move toward electrified mobility and expanded deployment of solar and wind on the electric grid. If those trends escalate as expected, the need for better methods of storing electrical energy will intensify.

    “We need all the strategies we can get to address the threat of climate change,” says Elsa Olivetti PhD ’07, the Esther and Harold E. Edgerton Associate Professor in Materials Science and Engineering. “Obviously, developing technologies for grid-based storage at a large scale is critical. But for mobile applications — in particular, transportation — much research is focusing on adapting today’s lithium-ion battery to make versions that are safer, smaller, and can store more energy for their size and weight.”

    Traditional lithium-ion batteries continue to improve, but they have limitations that persist, in part because of their structure. A lithium-ion battery consists of two electrodes — one positive and one negative — sandwiched around an organic (carbon-containing) liquid. As the battery is charged and discharged, electrically charged particles (or ions) of lithium pass from one electrode to the other through the liquid electrolyte.

    One problem with that design is that at certain voltages and temperatures, the liquid electrolyte can become volatile and catch fire. “Batteries are generally safe under normal usage, but the risk is still there,” says Kevin Huang PhD ’15, a research scientist in Olivetti’s group.

    Another problem is that lithium-ion batteries are not well-suited for use in vehicles. Large, heavy battery packs take up space and increase a vehicle’s overall weight, reducing fuel efficiency. But it’s proving difficult to make today’s lithium-ion batteries smaller and lighter while maintaining their energy density — that is, the amount of energy they store per gram of weight.

    To solve those problems, researchers are changing key features of the lithium-ion battery to make an all-solid, or “solid-state,” version. They replace the liquid electrolyte in the middle with a thin, solid electrolyte that’s stable at a wide range of voltages and temperatures. With that solid electrolyte, they use a high-capacity positive electrode and a high-capacity, lithium metal negative electrode that’s far thinner than the usual layer of porous carbon. Those changes make it possible to shrink the overall battery considerably while maintaining its energy-storage capacity, thereby achieving a higher energy density.

    “Those features — enhanced safety and greater energy density — are probably the two most-often-touted advantages of a potential solid-state battery,” says Huang. He then quickly clarifies that “all of these things are prospective, hoped-for, and not necessarily realized.” Nevertheless, the possibility has many researchers scrambling to find materials and designs that can deliver on that promise.

    Thinking beyond the lab

    Researchers have come up with many intriguing options that look promising — in the lab. But Olivetti and Huang believe that additional practical considerations may be important, given the urgency of the climate change challenge. “There are always metrics that we researchers use in the lab to evaluate possible materials and processes,” says Olivetti. Examples might include energy-storage capacity and charge/discharge rate. When performing basic research — which she deems both necessary and important — those metrics are appropriate. “But if the aim is implementation, we suggest adding a few metrics that specifically address the potential for rapid scaling,” she says.

    Based on industry’s experience with current lithium-ion batteries, the MIT researchers and their colleague Gerbrand Ceder, the Daniel M. Tellep Distinguished Professor of Engineering at the University of California at Berkeley, suggest three broad questions that can help identify potential constraints on future scale-up as a result of materials selection. First, with this battery design, could materials availability, supply chains, or price volatility become a problem as production scales up? (Note that the environmental and other concerns raised by expanded mining are outside the scope of this study.) Second, will fabricating batteries from these materials involve difficult manufacturing steps during which parts are likely to fail? And third, do manufacturing measures needed to ensure a high-performance product based on these materials ultimately lower or raise the cost of the batteries produced?

    To demonstrate their approach, Olivetti, Ceder, and Huang examined some of the electrolyte chemistries and battery structures now being investigated by researchers. To select their examples, they turned to previous work in which they and their collaborators used text- and data-mining techniques to gather information on materials and processing details reported in the literature. From that database, they selected a few frequently reported options that represent a range of possibilities.

    Materials and availability

    In the world of solid inorganic electrolytes, there are two main classes of materials — the oxides, which contain oxygen, and the sulfides, which contain sulfur. Olivetti, Ceder, and Huang focused on one promising electrolyte option in each class and examined key elements of concern for each of them.

    The sulfide they considered was LGPS, which combines lithium, germanium, phosphorus, and sulfur. Based on availability considerations, they focused on the germanium, an element that raises concerns in part because it’s not generally mined on its own. Instead, it’s a byproduct produced during the mining of coal and zinc.

    To investigate its availability, the researchers looked at how much germanium was produced annually in the past six decades during coal and zinc mining and then at how much could have been produced. The outcome suggested that 100 times more germanium could have been produced, even in recent years. Given that supply potential, the availability of germanium is not likely to constrain the scale-up of a solid-state battery based on an LGPS electrolyte.

    The situation looked less promising with the researchers’ selected oxide, LLZO, which consists of lithium, lanthanum, zirconium, and oxygen. Extraction and processing of lanthanum are largely concentrated in China, and there’s limited data available, so the researchers didn’t try to analyze its availability. The other three elements are abundantly available. However, in practice, a small quantity of another element — called a dopant — must be added to make LLZO easy to process. So the team focused on tantalum, the most frequently used dopant, as the main element of concern for LLZO.

    Tantalum is produced as a byproduct of tin and niobium mining. Historical data show that the amount of tantalum produced during tin and niobium mining was much closer to the potential maximum than was the case with germanium. So the availability of tantalum is more of a concern for the possible scale-up of an LLZO-based battery.

    But knowing the availability of an element in the ground doesn’t address the steps required to get it to a manufacturer. So the researchers investigated a follow-on question concerning the supply chains for critical elements — mining, processing, refining, shipping, and so on. Assuming that abundant supplies are available, can the supply chains that deliver those materials expand quickly enough to meet the growing demand for batteries?

    In sample analyses, they looked at how much supply chains for germanium and tantalum would need to grow year to year to provide batteries for a projected fleet of electric vehicles in 2030. As an example, an electric vehicle fleet often cited as a goal for 2030 would require production of enough batteries to deliver a total of 100 gigawatt hours of energy. To meet that goal using just LGPS batteries, the supply chain for germanium would need to grow by 50 percent from year to year — a stretch, since the maximum growth rate in the past has been about 7 percent. Using just LLZO batteries, the supply chain for tantalum would need to grow by about 30 percent — a growth rate well above the historical high of about 10 percent.

    Those examples demonstrate the importance of considering both materials availability and supply chains when evaluating different solid electrolytes for their scale-up potential. “Even when the quantity of a material available isn’t a concern, as is the case with germanium, scaling all the steps in the supply chain to match the future production of electric vehicles may require a growth rate that’s literally unprecedented,” says Huang.

    Materials and processing

    In assessing the potential for scale-up of a battery design, another factor to consider is the difficulty of the manufacturing process and how it may impact cost. Fabricating a solid-state battery inevitably involves many steps, and a failure at any step raises the cost of each battery successfully produced. As Huang explains, “You’re not shipping those failed batteries; you’re throwing them away. But you’ve still spent money on the materials and time and processing.”

    As a proxy for manufacturing difficulty, Olivetti, Ceder, and Huang explored the impact of failure rate on overall cost for selected solid-state battery designs in their database. In one example, they focused on the oxide LLZO. LLZO is extremely brittle, and at the high temperatures involved in manufacturing, a large sheet that’s thin enough to use in a high-performance solid-state battery is likely to crack or warp.

    To determine the impact of such failures on cost, they modeled four key processing steps in assembling LLZO-based batteries. At each step, they calculated cost based on an assumed yield — that is, the fraction of total units that were successfully processed without failing. With the LLZO, the yield was far lower than with the other designs they examined; and, as the yield went down, the cost of each kilowatt-hour (kWh) of battery energy went up significantly. For example, when 5 percent more units failed during the final cathode heating step, cost increased by about $30/kWh — a nontrivial change considering that a commonly accepted target cost for such batteries is $100/kWh. Clearly, manufacturing difficulties can have a profound impact on the viability of a design for large-scale adoption.

    Materials and performance

    One of the main challenges in designing an all-solid battery comes from “interfaces” — that is, where one component meets another. During manufacturing or operation, materials at those interfaces can become unstable. “Atoms start going places that they shouldn’t, and battery performance declines,” says Huang.

    As a result, much research is devoted to coming up with methods of stabilizing interfaces in different battery designs. Many of the methods proposed do increase performance; and as a result, the cost of the battery in dollars per kWh goes down. But implementing such solutions generally involves added materials and time, increasing the cost per kWh during large-scale manufacturing.

    To illustrate that trade-off, the researchers first examined their oxide, LLZO. Here, the goal is to stabilize the interface between the LLZO electrolyte and the negative electrode by inserting a thin layer of tin between the two. They analyzed the impacts — both positive and negative — on cost of implementing that solution. They found that adding the tin separator increases energy-storage capacity and improves performance, which reduces the unit cost in dollars/kWh. But the cost of including the tin layer exceeds the savings so that the final cost is higher than the original cost.

    In another analysis, they looked at a sulfide electrolyte called LPSCl, which consists of lithium, phosphorus, and sulfur with a bit of added chlorine. In this case, the positive electrode incorporates particles of the electrolyte material — a method of ensuring that the lithium ions can find a pathway through the electrolyte to the other electrode. However, the added electrolyte particles are not compatible with other particles in the positive electrode — another interface problem. In this case, a standard solution is to add a “binder,” another material that makes the particles stick together.

    Their analysis confirmed that without the binder, performance is poor, and the cost of the LPSCl-based battery is more than $500/kWh. Adding the binder improves performance significantly, and the cost drops by almost $300/kWh. In this case, the cost of adding the binder during manufacturing is so low that essentially all the of the cost decrease from adding the binder is realized. Here, the method implemented to solve the interface problem pays off in lower costs.

    The researchers performed similar studies of other promising solid-state batteries reported in the literature, and their results were consistent: The choice of battery materials and processes can affect not only near-term outcomes in the lab but also the feasibility and cost of manufacturing the proposed solid-state battery at the scale needed to meet future demand. The results also showed that considering all three factors together — availability, processing needs, and battery performance — is important because there may be collective effects and trade-offs involved.

    Olivetti is proud of the range of concerns the team’s approach can probe. But she stresses that it’s not meant to replace traditional metrics used to guide materials and processing choices in the lab. “Instead, it’s meant to complement those metrics by also looking broadly at the sorts of things that could get in the way of scaling” — an important consideration given what Huang calls “the urgent ticking clock” of clean energy and climate change.

    This research was supported by the Seed Fund Program of the MIT Energy Initiative (MITEI) Low-Carbon Energy Center for Energy Storage; by Shell, a founding member of MITEI; and by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Advanced Battery Materials Research Program. The text mining work was supported by the National Science Foundation, the Office of Naval Research, and MITEI.

    This article appears in the Spring 2021 issue of Energy Futures, the magazine of the MIT Energy Initiative. More

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    Using aluminum and water to make clean hydrogen fuel — when and where it’s needed

    As the world works to move away from fossil fuels, many researchers are investigating whether clean hydrogen fuel can play an expanded role in sectors from transportation and industry to buildings and power generation. It could be used in fuel cell vehicles, heat-producing boilers, electricity-generating gas turbines, systems for storing renewable energy, and more.

    But while using hydrogen doesn’t generate carbon emissions, making it typically does. Today, almost all hydrogen is produced using fossil fuel-based processes that together generate more than 2 percent of all global greenhouse gas emissions. In addition, hydrogen is often produced in one location and consumed in another, which means its use also presents logistical challenges.

    A promising reaction

    Another option for producing hydrogen comes from a perhaps surprising source: reacting aluminum with water. Aluminum metal will readily react with water at room temperature to form aluminum hydroxide and hydrogen. That reaction doesn’t typically take place because a layer of aluminum oxide naturally coats the raw metal, preventing it from coming directly into contact with water.

    Using the aluminum-water reaction to generate hydrogen doesn’t produce any greenhouse gas emissions, and it promises to solve the transportation problem for any location with available water. Simply move the aluminum and then react it with water on-site. “Fundamentally, the aluminum becomes a mechanism for storing hydrogen — and a very effective one,” says Douglas P. Hart, professor of mechanical engineering at MIT. “Using aluminum as our source, we can ‘store’ hydrogen at a density that’s 10 times greater than if we just store it as a compressed gas.”

    Two problems have kept aluminum from being employed as a safe, economical source for hydrogen generation. The first problem is ensuring that the aluminum surface is clean and available to react with water. To that end, a practical system must include a means of first modifying the oxide layer and then keeping it from re-forming as the reaction proceeds.

    The second problem is that pure aluminum is energy-intensive to mine and produce, so any practical approach needs to use scrap aluminum from various sources. But scrap aluminum is not an easy starting material. It typically occurs in an alloyed form, meaning that it contains other elements that are added to change the properties or characteristics of the aluminum for different uses. For example, adding magnesium increases strength and corrosion-resistance, adding silicon lowers the melting point, and adding a little of both makes an alloy that’s moderately strong and corrosion-resistant.

    Despite considerable research on aluminum as a source of hydrogen, two key questions remain: What’s the best way to prevent the adherence of an oxide layer on the aluminum surface, and how do alloying elements in a piece of scrap aluminum affect the total amount of hydrogen generated and the rate at which it is generated?

    “If we’re going to use scrap aluminum for hydrogen generation in a practical application, we need to be able to better predict what hydrogen generation characteristics we’re going to observe from the aluminum-water reaction,” says Laureen Meroueh PhD ’20, who earned her doctorate in mechanical engineering.

    Since the fundamental steps in the reaction aren’t well understood, it’s been hard to predict the rate and volume at which hydrogen forms from scrap aluminum, which can contain varying types and concentrations of alloying elements. So Hart, Meroueh, and Thomas W. Eagar, a professor of materials engineering and engineering management in the MIT Department of Materials Science and Engineering, decided to examine — in a systematic fashion — the impacts of those alloying elements on the aluminum-water reaction and on a promising technique for preventing the formation of the interfering oxide layer.

    To prepare, they had experts at Novelis Inc. fabricate samples of pure aluminum and of specific aluminum alloys made of commercially pure aluminum combined with either 0.6 percent silicon (by weight), 1 percent magnesium, or both — compositions that are typical of scrap aluminum from a variety of sources. Using those samples, the MIT researchers performed a series of tests to explore different aspects of the aluminum-water reaction.

    Pre-treating the aluminum

    The first step was to demonstrate an effective means of penetrating the oxide layer that forms on aluminum in the air. Solid aluminum is made up of tiny grains that are packed together with occasional boundaries where they don’t line up perfectly. To maximize hydrogen production, researchers would need to prevent the formation of the oxide layer on all those interior grain surfaces.

    Research groups have already tried various ways of keeping the aluminum grains “activated” for reaction with water. Some have crushed scrap samples into particles so tiny that the oxide layer doesn’t adhere. But aluminum powders are dangerous, as they can react with humidity and explode. Another approach calls for grinding up scrap samples and adding liquid metals to prevent oxide deposition. But grinding is a costly and energy-intensive process.

    To Hart, Meroueh, and Eagar, the most promising approach — first introduced by Jonathan Slocum ScD ’18 while he was working in Hart’s research group — involved pre-treating the solid aluminum by painting liquid metals on top and allowing them to permeate through the grain boundaries.

    To determine the effectiveness of that approach, the researchers needed to confirm that the liquid metals would reach the internal grain surfaces, with and without alloying elements present. And they had to establish how long it would take for the liquid metal to coat all of the grains in pure aluminum and its alloys.

    They started by combining two metals — gallium and indium — in specific proportions to create a “eutectic” mixture; that is, a mixture that would remain in liquid form at room temperature. They coated their samples with the eutectic and allowed it to penetrate for time periods ranging from 48 to 96 hours. They then exposed the samples to water and monitored the hydrogen yield (the amount formed) and flow rate for 250 minutes. After 48 hours, they also took high-magnification scanning electron microscope (SEM) images so they could observe the boundaries between adjacent aluminum grains.

    Based on the hydrogen yield measurements and the SEM images, the MIT team concluded that the gallium-indium eutectic does naturally permeate and reach the interior grain surfaces. However, the rate and extent of penetration vary with the alloy. The permeation rate was the same in silicon-doped aluminum samples as in pure aluminum samples but slower in magnesium-doped samples.

    Perhaps most interesting were the results from samples doped with both silicon and magnesium — an aluminum alloy often found in recycling streams. Silicon and magnesium chemically bond to form magnesium silicide, which occurs as solid deposits on the internal grain surfaces. Meroueh hypothesized that when both silicon and magnesium are present in scrap aluminum, those deposits can act as barriers that impede the flow of the gallium-indium eutectic.

    The experiments and images confirmed her hypothesis: The solid deposits did act as barriers, and images of samples pre-treated for 48 hours showed that permeation wasn’t complete. Clearly, a lengthy pre-treatment period would be critical for maximizing the hydrogen yield from scraps of aluminum containing both silicon and magnesium.

    Meroueh cites several benefits to the process they used. “You don’t have to apply any energy for the gallium-indium eutectic to work its magic on aluminum and get rid of that oxide layer,” she says. “Once you’ve activated your aluminum, you can drop it in water, and it’ll generate hydrogen — no energy input required.” Even better, the eutectic doesn’t chemically react with the aluminum. “It just physically moves around in between the grains,” she says. “At the end of the process, I could recover all of the gallium and indium I put in and use it again” — a valuable feature as gallium and (especially) indium are costly and in relatively short supply.

    Impacts of alloying elements on hydrogen generation

    The researchers next investigated how the presence of alloying elements affects hydrogen generation. They tested samples that had been treated with the eutectic for 96 hours; by then, the hydrogen yield and flow rates had leveled off in all the samples.

    The presence of 0.6 percent silicon increased the hydrogen yield for a given weight of aluminum by 20 percent compared to pure aluminum — even though the silicon-containing sample had less aluminum than the pure aluminum sample. In contrast, the presence of 1 percent magnesium produced far less hydrogen, while adding both silicon and magnesium pushed the yield up, but not to the level of pure aluminum.

    The presence of silicon also greatly accelerated the reaction rate, producing a far higher peak in the flow rate but cutting short the duration of hydrogen output. The presence of magnesium produced a lower flow rate but allowed the hydrogen output to remain fairly steady over time. And once again, aluminum with both alloying elements produced a flow rate between that of magnesium-doped and pure aluminum.

    Those results provide practical guidance on how to adjust the hydrogen output to match the operating needs of a hydrogen-consuming device. If the starting material is commercially pure aluminum, adding small amounts of carefully selected alloying elements can tailor the hydrogen yield and flow rate. If the starting material is scrap aluminum, careful choice of the source can be key. For high, brief bursts of hydrogen, pieces of silicon-containing aluminum from an auto junkyard could work well. For lower but longer flows, magnesium-containing scraps from the frame of a demolished building might be better. For results somewhere in between, aluminum containing both silicon and magnesium should work well; such material is abundantly available from scrapped cars and motorcycles, yachts, bicycle frames, and even smartphone cases.

    It should also be possible to combine scraps of different aluminum alloys to tune the outcome, notes Meroueh. “If I have a sample of activated aluminum that contains just silicon and another sample that contains just magnesium, I can put them both into a container of water and let them react,” she says. “So I get the fast ramp-up in hydrogen production from the silicon and then the magnesium takes over and has that steady output.”

    Another opportunity for tuning: Reducing grain size

    Another practical way to affect hydrogen production could be to reduce the size of the aluminum grains — a change that should increase the total surface area available for reactions to occur.

    To investigate that approach, the researchers requested specially customized samples from their supplier. Using standard industrial procedures, the Novelis experts first fed each sample through two rollers, squeezing it from the top and bottom so that the internal grains were flattened. They then heated each sample until the long, flat grains had reorganized and shrunk to a targeted size.

    In a series of carefully designed experiments, the MIT team found that reducing the grain size increased the efficiency and decreased the duration of the reaction to varying degrees in the different samples. Again, the presence of particular alloying elements had a major effect on the outcome.

    Needed: A revised theory that explains observations

    Throughout their experiments, the researchers encountered some unexpected results. For example, standard corrosion theory predicts that pure aluminum will generate more hydrogen than silicon-doped aluminum will — the opposite of what they observed in their experiments.

    To shed light on the underlying chemical reactions, Hart, Meroueh, and Eagar investigated hydrogen “flux,” that is, the volume of hydrogen generated over time on each square centimeter of aluminum surface, including the interior grains. They examined three grain sizes for each of their four compositions and collected thousands of data points measuring hydrogen flux.

    Their results show that reducing grain size has significant effects. It increases the peak hydrogen flux from silicon-doped aluminum as much as 100 times and from the other three compositions by 10 times. With both pure aluminum and silicon-containing aluminum, reducing grain size also decreases the delay before the peak flux and increases the rate of decline afterward. With magnesium-containing aluminum, reducing the grain size brings about an increase in peak hydrogen flux and results in a slightly faster decline in the rate of hydrogen output. With both silicon and magnesium present, the hydrogen flux over time resembles that of magnesium-containing aluminum when the grain size is not manipulated. When the grain size is reduced, the hydrogen output characteristics begin to resemble behavior observed in silicon-containing aluminum. That outcome was unexpected because when silicon and magnesium are both present, they react to form magnesium silicide, resulting in a new type of aluminum alloy with its own properties.

    The researchers stress the benefits of developing a better fundamental understanding of the underlying chemical reactions involved. In addition to guiding the design of practical systems, it might help them find a replacement for the expensive indium in their pre-treatment mixture. Other work has shown that gallium will naturally permeate through the grain boundaries of aluminum. “At this point, we know that the indium in our eutectic is important, but we don’t really understand what it does, so we don’t know how to replace it,” says Hart.

    But already Hart, Meroueh, and Eagar have demonstrated two practical ways of tuning the hydrogen reaction rate: by adding certain elements to the aluminum and by manipulating the size of the interior aluminum grains. In combination, those approaches can deliver significant results. “If you go from magnesium-containing aluminum with the largest grain size to silicon-containing aluminum with the smallest grain size, you get a hydrogen reaction rate that differs by two orders of magnitude,” says Meroueh. “That’s huge if you’re trying to design a real system that would use this reaction.”

    This research was supported through the MIT Energy Initiative by ExxonMobil-MIT Energy Fellowships awarded to Laureen Meroueh PhD ’20 from 2018 to 2020.

    This article appears in the Spring 2021 issue of Energy Futures, the magazine of the MIT Energy Initiative.  More

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    Elsa Olivetti wins 2021 MIT Bose Award for Excellence in Teaching

    This year’s Bose Award for Excellence in Teaching has been presented to MIT Associate Professor Elsa Olivetti. Olivetti’s zest for enhancing the student experience is evident in the innovative and creative flare she brings to all aspects of her work.

    “Professor Olivetti’s dedication to teaching is truly inspiring,” says Anantha P. Chandrakasan, dean of the School of Engineering and the Vannevar Bush Professor of Electrical Engineering and Computer Science. “She has an extraordinary ability to engage her students, and has developed transformational approaches to curriculum and mentoring.”

    Olivetti is the Esther and Harold E. Edgerton Associate Professor in Materials Science and Engineering, and co-director of the MIT Climate and Sustainability Consortium. Her passion for addressing issues related to climate change frames the focus of her research, which centers on improving the environmental and economic sustainability of materials in the context of growing global demand. Her work focuses on reducing the significant burden of materials production and consumption through increased use of recycled and waste materials; informing the early-stage design of new materials for effective scale-up; and understanding the implications of policy, new technology development, and manufacturing processes on materials supply chains. 

    Olivetti has made significant contributions on education within the Department of Materials Science and Engineering since she came on board in 2014, including designing and implementing a subject on industrial ecology and materials, co-design of the Advanced Materials Machines NEET program, and developing a new undergraduate curriculum. Underscoring the care she has for her students’ success and well-being, Olivetti also cultivated the Course 3 Industry Seminars, pairing undergraduates with individuals working in careers related to 3D printing, environmental consulting, and manufacturing, with the aim of assisting her students with employment opportunities.

    “Professor Olivetti is a brilliant teacher and a creative educator, who engages the classroom with an uncanny ability to keep students on the edge of their seats combined with a remarkable and signature style that creates learning moments they remember years later,” says Jeff Grossman, head of the Department of Materials Science and Engineering. “I am proud to have Elsa as a colleague, and I am delighted that her excellence has been recognized with the Bose Award.”

    Olivetti received her PhD in materials science and engineering from MIT in 2007; shortly after, she joined the department as a postdoc. She subsequently worked as a research scientist in the Materials Systems Lab from 2009 to 2013 and joined the DMSE faculty in 2014. She was recently named a 2021 MacVicar Faculty Fellow in recognition of her exceptional commitment to curricular innovation, scientific research, and improving the student experience through teaching, mentoring, and advising. Previously, she has received the Earll M. Murman Award for Excellence in Undergraduate Advising in 2017, the award for “best DMSE advisor” in 2019, and the Paul Gray Award for Public Service in 2020.

    The Bose Award for Excellence in Teaching is given annually to a faculty member whose contributions to education have been characterized by dedication, care, and creativity. Established in 1990 by the School of Engineering, the award stands as a tribute to the late Amar Bose, a professor of electrical engineering and computer science and the founder of the Bose Corporation, to recognize outstanding contributions to undergraduate education by members of its faculty. More

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    Using graphene foam to filter toxins from drinking water

    Some kinds of water pollution, such as algal blooms and plastics that foul rivers, lakes, and marine environments, lie in plain sight. But other contaminants are not so readily apparent, which makes their impact potentially more dangerous. Among these invisible substances is uranium. Leaching into water resources from mining operations, nuclear waste sites, or from natural subterranean deposits, the element can now be found flowing out of taps worldwide.

    In the United States alone, “many areas are affected by uranium contamination, including the High Plains and Central Valley aquifers, which supply drinking water to 6 million people,” says Ahmed Sami Helal, a postdoc in the Department of Nuclear Science and Engineering. This contamination poses a near and present danger. “Even small concentrations are bad for human health,” says Ju Li, the Battelle Energy Alliance Professor of Nuclear Science and Engineering and professor of materials science and engineering.

    Now, a team led by Li has devised a highly efficient method for removing uranium from drinking water. Applying an electric charge to graphene oxide foam, the researchers can capture uranium in solution, which precipitates out as a condensed solid crystal. The foam may be reused up to seven times without losing its electrochemical properties. “Within hours, our process can purify a large quantity of drinking water below the EPA limit for uranium,” says Li.

    A paper describing this work was published in this week Advanced Materials. The two first co-authors are Helal and Chao Wang, a postdoc at MIT during the study, who is now with the School of Materials Science and Engineering at Tongji University, Shanghai. Researchers from Argonne National Laboratory, Taiwan’s National Chiao Tung University, and the University of Tokyo also participated in the research. The Defense Threat Reduction Agency (U.S. Department of Defense) funded later stages of this work.

    Targeting the contaminant

    The project, launched three years ago, began as an effort to find better approaches to environmental cleanup of heavy metals from mining sites. To date, remediation methods for such metals as chromium, cadmium, arsenic, lead, mercury, radium, and uranium have proven limited and expensive. “These techniques are highly sensitive to organics in water, and are poor at separating out the heavy metal contaminants,” explains Helal. “So they involve long operation times, high capital costs, and at the end of extraction, generate more toxic sludge.”

    To the team, uranium seemed a particularly attractive target. Field testing from the U.S. Geological Service and the Environmental Protection Agency (EPA) has revealed unhealthy levels of uranium moving into reservoirs and aquifers from natural rock sources in the northeastern United States, from ponds and pits storing old nuclear weapons and fuel in places like Hanford, Washington, and from mining activities located in many western states. This kind of contamination is prevalent in many other nations as well. An alarming number of these sites show uranium concentrations close to or above the EPA’s recommended ceiling of 30 parts per billion (ppb) — a level linked to kidney damage, cancer risk, and neurobehavioral changes in humans.

    The critical challenge lay in finding a practical remediation process exclusively sensitive to uranium, capable of extracting it from solution without producing toxic residues. And while earlier research showed that electrically charged carbon fiber could filter uranium from water, the results were partial and imprecise.

    Wang managed to crack these problems — based on her investigation of the behavior of graphene foam used for lithium-sulfur batteries. “The physical performance of this foam was unique because of its ability to attract certain chemical species to its surface,” she says. “I thought the ligands in graphene foam would work well with uranium.”

    Simple, efficient, and clean

    The team set to work transforming graphene foam into the equivalent of a uranium magnet. They learned that by sending an electric charge through the foam, splitting water and releasing hydrogen, they could increase the local pH and induce a chemical change that pulled uranium ions out of solution. The researchers found that the uranium would graft itself onto the foam’s surface, where it formed a never-before-seen crystalline uranium hydroxide. On reversal of the electric charge, the mineral, which resembles fish scales, slipped easily off the foam.

    It took hundreds of tries to get the chemical composition and electrolysis just right. “We kept changing the functional chemical groups to get them to work correctly,” says Helal. “And the foam was initially quite fragile, tending to break into pieces, so we needed to make it stronger and more durable,” says Wang.

    This uranium filtration process is simple, efficient, and clean, according to Li: “Each time it’s used, our foam can capture four times its own weight of uranium, and we can achieve an extraction capacity of 4,000 mg per gram, which is a major improvement over other methods,” he says. “We’ve also made a major breakthrough in reusability, because the foam can go through seven cycles without losing its extraction efficiency.” The graphene foam functions as well in seawater, where it reduces uranium concentrations from 3 parts per million to 19.9 ppb, showing that other ions in the brine do not interfere with filtration.

    The team believes its low-cost, effective device could become a new kind of home water filter, fitting on faucets like those of commercial brands. “Some of these filters already have activated carbon, so maybe we could modify these, add low-voltage electricity to filter uranium,” says Li.

    “The uranium extraction this device achieves is very impressive when compared to existing methods,” says Ho Jin Ryu, associate professor of nuclear and quantum engineering at the Korea Advanced Institute of Science and Technology. Ryu, who was not involved in the research, believes that the demonstration of graphene foam reusability is a “significant advance,” and that “the technology of local pH control to enhance uranium deposition will be impactful because the scientific principle can be applied more generally to heavy metal extraction from polluted water.”

    The researchers have already begun investigating broader applications of their method. “There is a science to this, so we can modify our filters to be selective for other heavy metals such as lead, mercury, and cadmium,” says Li. He notes that radium is another significant danger for locales in the United States and elsewhere that lack resources for reliable drinking water infrastructure.

    “In the future, instead of a passive water filter, we could be using a smart filter powered by clean electricity that turns on electrolytic action, which could extract multiple toxic metals, tell you when to regenerate the filter, and give you quality assurance about the water you’re drinking.” More

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    Cleaning up industrial filtration

    If you wanted to get pasta out of a pot of water, would you boil off the water, or use a strainer? While home cooks would choose the strainer, many industries continue to use energy-intensive thermal methods of separating out liquids. In some cases, that’s because it’s difficult to make a filtration system for chemical separation, which requires pores small enough to separate atoms.

    In other cases, membranes exist to separate liquids, but they are made of fragile polymers, which can break down or gum up in industrial use.

    Via Separations, a startup that emerged from MIT in 2017, has set out to address these challenges with a membrane that is cost-effective and robust. Made of graphene oxide (a “cousin” of pencil lead), the membrane can reduce the amount of energy used in industrial separations by 90 percent, according to Shreya Dave PhD ’16, company co-founder and CEO.

    This is valuable because separation processes account for about 22 percent of all in-plant energy use in the United States, according to Oak Ridge National Laboratory. By making such processes significantly more efficient, Via Separations plans to both save energy and address the significant emissions produced by thermal processes. “Our goal is eliminating 500 megatons of carbon dioxide emissions by 2050,” Dave says.

    Play video

    What do our passions for pasta and decarbonizing the Earth have in common? MIT alumna Shreya Dave PhD ’16 explains how she and her team at Via Separations are building the equivalent of a pasta strainer to separate chemical compounds for industry.

    Via Separations began piloting its technology this year at a U.S. paper company and expects to deploy a full commercial system there in the spring of 2022. “Our vision is to help manufacturers slow carbon dioxide emissions next year,” Dave says.

    MITEI Seed Grant

    The story of Via Separations begins in 2012, when the MIT Energy Initiative (MITEI) awarded a Seed Fund grant to Professor Jeffrey Grossman, who is now the Morton and Claire Goulder and Family Professor in Environmental Systems and head of MIT’s Department of Materials Science and Engineering. Grossman was pursuing research into nanoporous membranes for water desalination. “We thought we could bring down the cost of desalination and improve access to clean water,” says Dave, who worked on the project as a graduate student in Grossman’s lab.

    There, she teamed up with Brent Keller PhD ’16, another Grossman graduate student and a 2016-17 ExxonMobil-MIT Energy Fellow, who was developing lab experiments to fabricate and test new materials. “We were early comrades in figuring out how to debug experiments or fix equipment,” says Keller, Via Separations’ co-founder and chief technology officer. “We were fast friends who spent a lot of time talking about science over burritos.”

    Dave went on to write her doctoral thesis on using graphene oxide for water desalination, but that turned out to be the wrong application of the technology from a business perspective, she says. “The cost of desalination doesn’t lie in the membrane materials,” she explains.

    So, after Dave and Keller graduated from MIT in 2016, they spent a lot of time talking to customers to learn more about the needs and opportunities for their new separation technology. This research led them to target the paper industry, because the environmental benefits of improving paper processing are enormous, Dave says. “The paper industry is particularly exciting because separation processes just in that industry account for more than 2 percent of U.S. energy consumption,” she says. “It’s a very concentrated, high-energy-use industry.”

    Most paper today is made by breaking down the chemical bonds in wood to create wood pulp, the primary ingredient of paper. This process generates a byproduct called black liquor, a toxic solution that was once simply dumped into waterways. To clean up this process, paper mills turned to boiling off the water from black liquor and recovering both water and chemicals for reuse in the pulping process. (Today, the most valuable way to use the liquor is as biomass feedstock to generate energy.) Via Separations plans to accomplish this same separation work by filtering black liquor through its graphene oxide membrane.

    “The advantage of graphene oxide is that it’s very robust,” Dave says. “It’s got carbon double bonds that hold together in a lot of environments, including at different pH levels and temperatures that are typically unfriendly to materials.”

    Such properties should also make the company’s membranes attractive to other industries that use membrane separation, Keller says, because today’s polymer membranes have drawbacks. “For most of the things we make — from plastics to paper and gasoline — those polymers will swell or react or degrade,” he says.

    Graphene oxide is significantly more durable, and Via Separations can customize the pores in the material to suit each industry’s application. “That’s our secret sauce,” Dave says, “modulating pore size while retaining robustness to operate in challenging environments.”

    “We’re building a catalog of products to serve different applications,” Keller says, noting that the next target market could be the food and beverage industry. “In that industry, instead of separating different corrosive paper chemicals from water, we’re trying to separate particular sugars and food ingredients from other things.”

    Future target customers include pharmaceutical companies, oil refineries, and semiconductor manufacturers, or even carbon capture businesses.

    Scaling up

    Dave, Keller, and Grossman launched Via Separations in 2017 — with a lot of help from MIT. After the seed grant, in 2015, the founders received a year of funding and support from the J-WAFS Solutions program to explore markets and to develop their business plans. The company’s first capital investment came from The Engine, a venture firm founded by MIT to support “tough tech” companies (tech businesses with transformative potential but long and challenging paths to success). They also received advice and support from MIT’s Deshpande Center for Technological Innovation, Venture Mentoring Service, and Technology Licensing Office. In addition, Grossman continues to serve the company as chief scientist.

    “We were incredibly fortunate to be starting a company in the MIT entrepreneurial ecosystem,” Keller says, noting that The Engine support alone “probably shaved years off our progress.”

    Already, Via Separations has grown to employ 17 people, while significantly scaling up its product. “Our customers are producing thousands of gallons per minute,” Keller explains. “To process that much liquid, we need huge areas of membrane.”

    Via Separations’ manufacturing process, which is now capable of making more than 10,000 square feet of membrane in one production run, is a key competitive advantage, Dave says. The company rolls 300-400 square feet of membrane into a module, and modules can be combined as needed to increase filtration capacity.

    The goal, Dave says, is to contribute to a more sustainable world by making an environmentally beneficial product that makes good business sense. “What we do is make manufacturing things more energy-efficient,” she says. “We allow a paper mill or chemical facility to make more product using less energy and with lower costs. So, there is a bottom-line benefit that’s significant on an industrial scale.”

    Keller says he shares Dave’s goal of building a more sustainable future. “Climate change and energy are central challenges of our time,” he says. “Working on something that has a chance to make a meaningful impact on something so important to everyone is really fulfilling.”

    This article appears in the Spring 2021 issue of Energy Futures, the magazine of the MIT Energy Initiative.  More

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    Investigating materials for safe, secure nuclear power

    Michael Short came to MIT in the fall of 2001 as an 18-year-old first-year who grew up in Boston’s North Shore. He immediately felt at home, so much so that he’s never really left. It’s not that Short has no interest in exploring the world beyond the confines of the Institute, as he is an energetic and venturesome fellow. It’s just that almost everything he hopes to achieve in his scientific career can, in his opinion, be best pursued at this university.

    Last year — after collecting four MIT degrees and joining the faculty of the Department of Nuclear Science and Engineering (NSE) in 2013 — he was promoted to the status of tenured associate professor.

    Short’s enthusiasm for MIT began early in high school when he attended weekend programs that were mainly taught by undergraduates. “It was a program filled with my kind of people,” he recalls. “My high school was very good, but this was at a different level — at the level I was seeking and hoping to achieve. I felt more at home here than I did in my hometown, and the Saturdays at MIT were the highlight of my week.” He loved his four-year experience as an MIT undergraduate, including the research he carried out in the Uhlig Corrosion Laboratory, and he wasn’t ready for it to end.

    After graduating in 2005 with two BS degrees (one in NSE and another in materials science and engineering), he took on some computer programming jobs and worked half time in the Uhlig lab under the supervision of Ronald Ballinger, a professor in both NSE and the Department of Materials Science and Engineering. Short soon realized that computer programming was not for him, and he started graduate studies with Ballinger as his advisor, earning a master’s and a PhD in nuclear science and engineering in 2010.

    Even as an undergraduate, Short was convinced that nuclear power was essential to our nation’s (and the world’s) energy future, especially in light of the urgent need to move toward carbon-free sources of power. During his first year, he was told by Ballinger that the main challenge confronting nuclear power was to find materials, and metals in particular, that could last long enough in the face of radiation and the chemically destructive effects of corrosion.

    Those words, persuasively stated, led him to his double major.  “Materials and radiation damage have been at the core of my research ever since,” Short says. “Remarkably, the stuff I started studying in my first year of college is what I do today, though I’ve extended this work in many directions.”

    Corrosion has proven to be an unexpectedly rich subject. “The traditional view is to expose metals to various things and see what happens — ‘cook and look,’ as it’s called,” he says. “A lot of folks view it that way, but it’s actually much more complex. In fact, some members of our own faculty don’t want to touch corrosion because it’s too complicated, too dirty. But that’s what I like about it.”

    In a 2020 paper published in Nature Communications, Short, his student Weiyue Zhou, and other colleagues made a surprising discovery. “Most people think radiation is bad and makes everything worse, but that’s not always the case,” Short maintains. His team found a specific set of conditions under which a metal (a nickel-chromium alloy) performs better when it is irradiated while undergoing corrosion in a molten salt mixture. Their finding is relevant, he adds, “because these are the conditions under which people are hoping to run the next generation of nuclear reactors.” Leading candidates for alternatives to today’s water-cooled reactors are molten salt and liquid metal (specifically liquid lead and sodium) cooled reactors. To this end, Short and his colleagues are currently carrying out similar experiments involving the irradiation of metal alloys immersed in liquid lead.

    Meanwhile, Short has pursued another multiyear project, trying to devise a new standard to serve as “a measurable unit of radiation damage.” In fact, these were the very words he wrote on his research statement when applying for his first faculty position at MIT, although he admits that he didn’t know then how to realize that goal. But the effort is finally paying off, as Short and his collaborators are about to submit their first big paper on the topic. He’s found that you can’t reduce radiation damage to a single number, which is what people have tried to do in the past, because that’s too simple. Instead, their new standard relates to the density of defects — the number of radiation-induced defects (or unintentional changes to the lattice structure) per unit volume for a given material.

    “Our approach is based on a theory that everyone agrees on — that defects have energy,” Short explains. However, many people told him and his team that the amount of energy stored within those defects would be too small to measure. But that just spurred them to try harder, making measurements at the microjoule level, at the very limits of detection.

    Short is convinced that their new standard will become “universally useful, but it will take years of testing on many, many materials followed by more years of convincing people using the classic method: Repeat, repeat, repeat, making sure that each time you get the same result. It’s the unglamorous side of science, but that’s the side that really matters.”

    The approach has already led Short, in collaboration with NSE proliferation expert Scott Kemp, into the field of nuclear security. Equipped with new insights into the signatures left behind by radiation damage, students co-supervised by Kemp and Short have devised methods for determining how much fissionable material has passed through a uranium enrichment facility, for example, by scrutinizing the materials exposed to these radioactive substances. “I never thought my preliminary work on corrosion experiments as an undergraduate would lead to this,” Short says.

    He has also turned his attention to “microreactors” — nuclear reactors with power ratings as small as a single megawatt, as compared to the 1,000-megawatt behemoths of today. Flexibility in the size of future power plants is essential to the economic viability of nuclear power, he insists, “because nobody wants to pay $10 billion for a reactor now, and I don’t blame them.”

    But the proposed microreactors, he says, “pose new material challenges that I want to solve. It comes down to cramming more material into a smaller volume, and we don’t have a lot of knowledge about how materials perform at such high densities.” Short is currently conducting experiments with the Idaho National Laboratory, irradiating possible microreactor materials to see how they change using a laser technique, transient grating spectroscopy (TGS), which his MIT group has had a big hand in advancing.

    It’s been an exhilarating 20 years at MIT for Short, and he has even more ambitious goals for the next 20 years. “I’d like to be one of those who came up with a way to verify the Iran nuclear deal and thereby helped clamp down on nuclear proliferation worldwide,” he says. “I’d like to choose the materials for our first power-generating nuclear fusion reactors. And I’d like to have influenced perhaps 50 to 100 former students who chose to stay in science because they truly enjoy it.

    “I see my job as creating scientists, not science,” he says, “though science is, of course, a convenient byproduct.” More

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    A material difference

    Eesha Khare has always seen a world of matter. The daughter of a hardware engineer and a biologist, she has an insatiable interest in what substances — both synthetic and biological — have in common. Not surprisingly, that perspective led her to the study of materials.

    “I recognized early on that everything around me is a material,” she says. “How our phones respond to touches, how trees in nature to give us both structural wood and foldable paper, or how we are able to make high skyscrapers with steel and glass, it all comes down to the fundamentals: This is materials science and engineering.”

    As a rising fourth-year PhD student in the MIT Department of Materials Science and Engineering (DMSE), Khare now studies the metal-coordination bonds that allow mussels to bind to rocks along turbulent coastlines. But Khare’s scientific enthusiasm has also led to expansive interests from science policy to climate advocacy and entrepreneurship.

    A material world

    A Silicon Valley native, Khare recalls vividly how excited she was about science as a young girl, both at school and at myriad science fairs and high school laboratory internships. One such internship at the University of California at Santa Cruz introduced her to the study of nanomaterials, or materials that are smaller than a single human cell. The project piqued her interest in how research could lead to energy-storage applications, and she began to ponder the connections between materials, science policy, and the environment.

    As an undergraduate at Harvard University, Khare pursued a degree in engineering sciences and chemistry while also working at the Harvard Kennedy School Institute of Politics. There, she grew fascinated by environmental advocacy in the policy space, working for then-professor Gina McCarthy, who is currently serving in the Biden administration as the first-ever White House climate advisor.

    Following her academic explorations in college, Khare wanted to consider science in a new light before pursuing her doctorate in materials science and engineering. She deferred her program acceptance at MIT in order to attend Cambridge University in the U.K., where she earned a master’s degree in the history and philosophy of science. “Especially in a PhD program, it can often feel like your head is deep in the science as you push new research frontiers, but I wanted take a step back and be inspired by how scientists in the past made their discoveries,” she says.

    Her experience at Cambridge was both challenging and informative, but Khare quickly found that her mechanistic curiosity remained persistent — a realization that came in the form of a biological material.

    “My very first master’s research project was about environmental pollution indicators in the U.K., and I was looking specifically at lichen to understand the social and political reasons why they were adopted by the public as pollution indicators,” Khare explains. “But I found myself wondering more about how lichen can act as pollution indicators. And I found that to be quite similar for most of my research projects: I was more interested in how the technology or discovery actually worked.”

    Enthusiasm for innovation

    Fittingly, these bioindicators confirmed for her that studying materials at MIT was the right course. Now Khare works on a different organism altogether, conducting research on the metal-coordination chemical interactions of a biopolymer secreted by mussels.

    “Mussels secrete this thread and can adhere to ocean walls. So, when ocean waves come, mussels don’t get dislodged that easily,” Khare says. “This is partly because of how metal ions in this material bind to different amino acids in the protein. There’s no input from the mussel itself to control anything there; all the magic is in this biological material that is not only very sticky, but also doesn’t break very readily, and if you cut it, it can re-heal that interface as well! If we could better understand and replicate this biological material in our own world, we could have materials self-heal and never break and thus eliminate so much waste.”

    To study this natural material, Khare combines computational and experimental techniques, experimentally synthesizing her own biopolymers and studying their properties with in silico molecular dynamics. Her co-advisors — Markus Buehler, the Jerry McAfee Professor of Engineering in Civil and Environmental Engineering, and Niels Holten-Andersen, professor of materials science and engineering — have embraced this dual-approach to her project, as well as her abundant enthusiasm for innovation.

    Khare likes to take one exploratory course per semester, and a recent offering in the MIT Sloan School of Management inspired her to pursue entrepreneurship. These days she is spending much of her free time on a startup called Taxie, formed with fellow MIT students after taking the course 15.390 (New Enterprises). Taxie attempts to electrify the rideshare business by making electric rental cars available to rideshare drivers. Khare hopes this project will initiate some small first steps in making the ridesharing industry environmentally cleaner — and in democratizing access to electric vehicles for rideshare drivers, who often hail from lower-income or immigrant backgrounds.

    “There are a lot of goals thrown around for reducing emissions or helping our environment. But we are slowly getting physical things on the road, physical things to real people, and I like to think that we are helping to accelerate the electric transition,” Khare says. “These small steps are helpful for learning, at the very least, how we can make a transition to electric or to a cleaner industry.”

    Alongside her startup work, Khare has pursued a number of other extracurricular activities at MIT, including co-organizing her department’s Student Application Assistance Program and serving on DMSE’s Diversity, Equity, and Inclusion Council. Her varied interests also have led to a diverse group of friends, which suits her well, because she is a self-described “people-person.”

    In a year where maintaining connections has been more challenging than usual, Khare has focused on the positive, spending her spring semester with family in California and practicing Bharatanatyam, a form of Indian classical dance, over Zoom. As she looks to the future, Khare hopes to bring even more of her interests together, like materials science and climate.

    “I want to understand the energy and environmental sector at large to identify the most pressing technology gaps and how can I use my knowledge to contribute. My goal is to figure out where can I personally make a difference and where it can have a bigger impact to help our climate,” she says. “I like being outside of my comfort zone.” More