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      Designing better batteries for electric vehicles

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      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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      Vapor-collection technology saves water while clearing the air

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      About two-fifths of all the water that gets withdrawn from lakes, rivers, and wells in the U.S. is used not for agriculture, drinking, or sanitation, but to cool the power plants that provide electricity from fossil fuels or nuclear power. Over 65 percent of these plants use evaporative cooling, leading to huge white plumes that billow from their cooling towers, which can be a nuisance and, in some cases, even contribute to dangerous driving conditions.

      Now, a small company based on technology recently developed at MIT by the Varanasi Research Group is hoping to reduce both the water needs at these plants and the resultant plumes — and to potentially help alleviate water shortages in areas where power plants put pressure on local water systems.

      The technology is surprisingly simple in principle, but developing it to the point where it can now be tested at full scale on industrial plants was a more complex proposition. That required the real-world experience that the company’s founders gained from installing prototype systems, first on MIT’s natural-gas-powered cogeneration plant and then on MIT’s nuclear research reactor.

      In these demanding tests, which involved exposure to not only the heat and vibrations of a working industrial plant but also the rigors of New England winters, the system proved its effectiveness at both eliminating the vapor plume and recapturing water. And, it purified the water in the process, so that it was 100 times cleaner than the incoming cooling water. The system is now being prepared for full-scale tests in a commercial power plant and in a chemical processing plant.

      “Campus as a living laboratory”

      The technology was originally envisioned by professor of mechanical engineering Kripa Varanasi to develop efficient water-recovery systems by capturing water droplets from both natural fog and plumes from power plant cooling towers. The project began as part of doctoral thesis research of Maher Damak PhD ’18, with funding from the MIT Tata Center for Technology and Design, to improve the efficiency of fog-harvesting systems like the ones used in some arid coastal regions as a source of potable water. Those systems, which generally consist of plastic or metal mesh hung vertically in the path of fogbanks, are extremely inefficient, capturing only about 1 to 3 percent of the water droplets that pass through them.

      Varanasi and Damak found that vapor collection could be made much more efficient by first zapping the tiny droplets of water with a beam of electrically charged particles, or ions, to give each droplet a slight electric charge. Then, the stream of droplets passes through a wire mesh, like a window screen, that has an opposite electrical charge. This causes the droplets to be strongly attracted to the mesh, where they fall away due to gravity and can be collected in trays placed below the mesh.

      Lab tests showed the concept worked, and the researchers, joined by Karim Khalil PhD ’18, won the MIT $100K Entrepreneurship Competition in 2018 for the basic concept. The nascent company, which they called Infinite Cooling, with Damak as CEO, Khalil as CTO, and Varanasi as chairperson, immediately went to work setting up a test installation on one of the cooling towers of MIT’s natural-gas-powered Central Utility Plant, with funding from the MIT Office of Sustainability. After experimenting with various configurations, they were able to show that the system could indeed eliminate the plume and produce water of high purity.

      Professor Jacopo Buongiorno in the Department of Nuclear Science and Engineering immediately spotted a good opportunity for collaboration, offering the use of MIT’s Nuclear Reactor Laboratory research facility for further testing of the system with the help of NRL engineer Ed Block. With its 24/7 operation and its higher-temperature vapor emissions, the plant would provide a more stringent real-world test of the system, as well as proving its effectiveness in an actual operating reactor licensed by the Nuclear Regulatory Commission, an important step in “de-risking” the technology so that electric utilities could feel confident in adopting the system.

      After the system was installed above one of the plant’s four cooling towers, testing showed that the water being collected was more than 100 times cleaner than the feedwater coming into the cooling system. It also proved that the installation — which, unlike the earlier version, had its mesh screens mounted vertically, parallel to the vapor stream — had no effect at all on the operation of the plant. Video of the tests dramatically illustrates how as soon as the power is switched on to the collecting mesh, the white plume of vapor immediately disappears completely.

      The high temperature and volume of the vapor plume from the reactor’s cooling towers represented “kind of a worst-case scenario in terms of plumes,” Damak says, “so if we can capture that, we can basically capture anything.”

      Working with MIT’s Nuclear Reactor Laboratory, Varanasi says, “has been quite an important step because it helped us to test it at scale. … It really both validated the water quality and the performance of the system.” The process, he says, “shows the importance of using the campus as a living laboratory. It allows us to do these kinds of experiments at scale, and also showed the ability to sustainably reduce the water footprint of the campus.”

      Far-reaching benefits

      Power plant plumes are often considered an eyesore and can lead to local opposition to new power plants because of the potential for obscured views, and even potential traffic hazards when the obscuring plumes blow across roadways. “The ability to eliminate the plumes could be an important benefit, allowing plants to be sited in locations that might otherwise be restricted,” Buongiorno says. At the same time, the system could eliminate a significant amount of water used by the plants and then lost to the sky, potentially alleviating pressure on local water systems, which could be especially helpful in arid regions.

      The system is essentially a distillation process, and the pure water it produces could go into power plant boilers — which are separate from the cooling system — that require high-purity water. That might reduce the need for both fresh water and purification systems for the boilers.

      What’s more, in many arid coastal areas power plants are cooled directly with seawater. This system would essentially add a water desalination capability to the plant, at a fraction of the cost of building a new standalone desalination plant, and at an even smaller fraction of its operating costs since the heat would essentially be provided for free.

      Contamination of water is typically measured by testing its electrical conductivity, which increases with the amount of salts and other contaminants it contains. Water used in power plant cooling systems typically measures 3,000 microsiemens per centimeter, Khalil explains, while the water supply in the City of Cambridge is typically around 500 or 600 microsiemens per centimeter. The water captured by this system, he says, typically measures below 50 microsiemens per centimeter.

      Thanks to the validation provided by the testing on MIT’s plants, the company has now been able to secure arrangements for its first two installations on operating commercial plants, which should begin later this year. One is a 900-megawatt power plant where the system’s clean water production will be a major advantage, and the other is at a chemical manufacturing plant in the Midwest.

      In many locations power plants have to pay for the water they use for cooling, Varanasi says, and the new system is expected to reduce the need for water by up to 20 percent. For a typical power plant, that alone could account for about a million dollars saved in water costs per year, he says.

      “Innovation has been a hallmark of the U.S. commercial industry for more than six decades,” says Maria G. Korsnick, president and CEO of the Nuclear Energy Institute, who was not involved in the research. “As the changing climate impacts every aspect of life, including global water supplies, companies across the supply chain are innovating for solutions. The testing of this innovative technology at MIT provides a valuable basis for its consideration in commercial applications.” More

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      Cleaning up industrial filtration

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      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