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    Study of disordered rock salts leads to battery breakthrough

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    For the past decade, disordered rock salt has been studied as a potential breakthrough cathode material for use in lithium-ion batteries and a key to creating low-cost, high-energy storage for everything from cell phones to electric vehicles to renewable energy storage.A new MIT study is making sure the material fulfills that promise.Led by Ju Li, the Tokyo Electric Power Company Professor in Nuclear Engineering and professor of materials science and engineering, a team of researchers describe a new class of partially disordered rock salt cathode, integrated with polyanions — dubbed disordered rock salt-polyanionic spinel, or DRXPS — that delivers high energy density at high voltages with significantly improved cycling stability.“There is typically a trade-off in cathode materials between energy density and cycling stability … and with this work we aim to push the envelope by designing new cathode chemistries,” says Yimeng Huang, a postdoc in the Department of Nuclear Science and Engineering and first author of a paper describing the work published today in Nature Energy. “(This) material family has high energy density and good cycling stability because it integrates two major types of cathode materials, rock salt and polyanionic olivine, so it has the benefits of both.”Importantly, Li adds, the new material family is primarily composed of manganese, an earth-abundant element that is significantly less expensive than elements like nickel and cobalt, which are typically used in cathodes today.“Manganese is at least five times less expensive than nickel, and about 30 times less expensive than cobalt,” Li says. “Manganese is also the one of the keys to achieving higher energy densities, so having that material be much more earth-abundant is a tremendous advantage.”A possible path to renewable energy infrastructureThat advantage will be particularly critical, Li and his co-authors wrote, as the world looks to build the renewable energy infrastructure needed for a low- or no-carbon future.Batteries are a particularly important part of that picture, not only for their potential to decarbonize transportation with electric cars, buses, and trucks, but also because they will be essential to addressing the intermittency issues of wind and solar power by storing excess energy, then feeding it back into the grid at night or on calm days, when renewable generation drops.Given the high cost and relative rarity of materials like cobalt and nickel, they wrote, efforts to rapidly scale up electric storage capacity would likely lead to extreme cost spikes and potentially significant materials shortages.“If we want to have true electrification of energy generation, transportation, and more, we need earth-abundant batteries to store intermittent photovoltaic and wind power,” Li says. “I think this is one of the steps toward that dream.”That sentiment was shared by Gerbrand Ceder, the Samsung Distinguished Chair in Nanoscience and Nanotechnology Research and a professor of materials science and engineering at the University of California at Berkeley.“Lithium-ion batteries are a critical part of the clean energy transition,” Ceder says. “Their continued growth and price decrease depends on the development of inexpensive, high-performance cathode materials made from earth-abundant materials, as presented in this work.”Overcoming obstacles in existing materialsThe new study addresses one of the major challenges facing disordered rock salt cathodes — oxygen mobility.While the materials have long been recognized for offering very high capacity — as much as 350 milliampere-hour per gram — as compared to traditional cathode materials, which typically have capacities of between 190 and 200 milliampere-hour per gram, it is not very stable.The high capacity is contributed partially by oxygen redox, which is activated when the cathode is charged to high voltages. But when that happens, oxygen becomes mobile, leading to reactions with the electrolyte and degradation of the material, eventually leaving it effectively useless after prolonged cycling.To overcome those challenges, Huang added another element — phosphorus — that essentially acts like a glue, holding the oxygen in place to mitigate degradation.“The main innovation here, and the theory behind the design, is that Yimeng added just the right amount of phosphorus, formed so-called polyanions with its neighboring oxygen atoms, into a cation-deficient rock salt structure that can pin them down,” Li explains. “That allows us to basically stop the percolating oxygen transport due to strong covalent bonding between phosphorus and oxygen … meaning we can both utilize the oxygen-contributed capacity, but also have good stability as well.”That ability to charge batteries to higher voltages, Li says, is crucial because it allows for simpler systems to manage the energy they store.“You can say the quality of the energy is higher,” he says. “The higher the voltage per cell, then the less you need to connect them in series in the battery pack, and the simpler the battery management system.”Pointing the way to future studiesWhile the cathode material described in the study could have a transformative impact on lithium-ion battery technology, there are still several avenues for study going forward.Among the areas for future study, Huang says, are efforts to explore new ways to fabricate the material, particularly for morphology and scalability considerations.“Right now, we are using high-energy ball milling for mechanochemical synthesis, and … the resulting morphology is non-uniform and has small average particle size (about 150 nanometers). This method is also not quite scalable,” he says. “We are trying to achieve a more uniform morphology with larger particle sizes using some alternate synthesis methods, which would allow us to increase the volumetric energy density of the material and may allow us to explore some coating methods … which could further improve the battery performance. The future methods, of course, should be industrially scalable.”In addition, he says, the disordered rock salt material by itself is not a particularly good conductor, so significant amounts of carbon — as much as 20 weight percent of the cathode paste — were added to boost its conductivity. If the team can reduce the carbon content in the electrode without sacrificing performance, there will be higher active material content in a battery, leading to an increased practical energy density.“In this paper, we just used Super P, a typical conductive carbon consisting of nanospheres, but they’re not very efficient,” Huang says. “We are now exploring using carbon nanotubes, which could reduce the carbon content to just 1 or 2 weight percent, which could allow us to dramatically increase the amount of the active cathode material.”Aside from decreasing carbon content, making thick electrodes, he adds, is yet another way to increase the practical energy density of the battery. This is another area of research that the team is working on.“This is only the beginning of DRXPS research, since we only explored a few chemistries within its vast compositional space,” he continues. “We can play around with different ratios of lithium, manganese, phosphorus, and oxygen, and with various combinations of other polyanion-forming elements such as boron, silicon, and sulfur.”With optimized compositions, more scalable synthesis methods, better morphology that allows for uniform coatings, lower carbon content, and thicker electrodes, he says, the DRXPS cathode family is very promising in applications of electric vehicles and grid storage, and possibly even in consumer electronics, where the volumetric energy density is very important.This work was supported with funding from the Honda Research Institute USA Inc. and the Molecular Foundry at Lawrence Berkeley National Laboratory, and used resources of the National Synchrotron Light Source II at Brookhaven National Laboratory and the Advanced Photon Source at Argonne National Laboratory.  More

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      A lasting — and valuable — legacy

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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      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