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      in Energy

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

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

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

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

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

      Going with the flow

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

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

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

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

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

      Multidisciplinary collaborators

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

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

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

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

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

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

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

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

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

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

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

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

    • 138 Shares169 Views

      in Environment

      Making catalytic surfaces more active to help decarbonize fuels and chemicals

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

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

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

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

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

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

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

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

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

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

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

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

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