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Materials Science Research Lecture

Wednesday, March 5, 2025
4:00pm to 5:00pm
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Noyes 147 (J. Holmes Sturdivant Lecture Hall)
Spin Probes and Materials Design for Next-Generation Li-ion Cathodes
Raphaele Clement, Associate Professor, Materials Science, UCSB,

***Refreshments at 3:45pm in Noyes lobby

Abstract:
While batteries have become ubiquitous in our daily lives, rapid growth in demand requires the development of higher energy density devices, and lower cost and more sustainable battery chemistries. When it comes to Li-ion batteries, despite significant research efforts over decades, we continue to rely on a limited subset of cathode materials that derive from the layered LiCoO2 oxide developed in 1980. The main bottleneck to advancing cathodes is the exceptional complexity of charge-discharge processes. This is compounded by the dearth of experimental techniques capable of bridging atomic-level phenomena and electrode-level performance.

In the first part of this talk, I will present our work combining advanced ex situ and operando characterization and first principles calculations to better understand the working principles and sources of irreversibility in LiNiO2. [1, 2]

The second part of this talk will focus on sustainable alternatives to commercial layered oxide cathodes. Disordered rocksalt oxides (DRX) are promising cathodes for next generation Li-ion batteries as they demonstrate high theoretical energy densities while enabling Co- and Ni- free chemistries. Our recent work has focused on Mn-based DRX cathodes, Li1+xMnyM'1-x-yO2-zFz (M' = Ti, Zr, Nb), and seeks to identify the links between composition, cation short-range order, and structural evolution during cycling, with significant impacts on specific capacity and capacity retention. [3, 4] We have specifically been interested in understanding the compositional parameters that affect the rate and extent of the "δ phase" transformation taking place in Mn-rich DRX (y > 0.5) during electrochemical cycling, resulting in the emergence of spinel-like domains within the long-range disordered structure and significant capacity activation. [5] I will also present solid-state microwave synthesis as a promising, non-equilibrium route towards micrometer-sized DRX cathodes with exceptional capacity retention. [6] This time- and energy-efficient route is scalable and represents a significant step toward the commercialization of inexpensive DRX Li-ion cathodes. A common theme throughout is the combined use of solid-state NMR, magnetometry, X-ray diffraction, and first principles calculations to better understand the links between synthesis, composition/structure and electrochemical properties.

[1] Nguyen, H., Kurzhals, P., Bianchini, M., Seidel, K., Clément, R., "New insights into aging in LiNiO2 cathodes from high resolution paramagnetic NMR spectroscopy", ChemComm, 60(35), 4707-4710 (2024).

[2] Nguyen, H., Silverstein, R., Zaveri, A., Cui, W., Kurzhals, P., Sicolo, S., Bianchini, M., Seidel, K., Clément, R., "Twin Boundaries Contribute to The First Cycle Irreversibility of LiNiO2", Adv. Funct. Mater., 2306168 (2023).

[3] Giovine, R., Yoshida, E., Ji, Y., Wu, V., Crafton, M., Ahn, J., Chen, G., McCloskey, B., Clément, R., Chem. Mater., 36, 3643-3654 (2024).

[4] Wu, V., Zhong, P., Ong, J., Yoshida, E., Kwon, A., Ceder, G., Clément, R., ACS Energy Lett., 9, 3027-3035 (2024).

[5] Li, T., Geraci, T., Koirala, K., Zohar, A., Bassey, E., Chater, P., Wang, C., Navrotsky, A., Clément, R., J. Am. Chem. Soc., 146, 24296–24309 (2024).

[6] Wu, V., Evans, H., Giovine, R., Preefer, M., Ong, J., Yoshida, E., Cabelguen, P.-E., Clément, R., Adv. Energy Mater., 13, 2203860 (2023).

More about the Speaker:

Raphaële Clément is an Associate Professor in Materials at UC Santa Barbara. She received her Ph.D. in Chemistry in 2016 from the University of Cambridge, working with Prof. Dame Clare Grey. She then joined the group of Prof. Gerbrand Ceder as a postdoc at UC Berkeley.

Prof. Clément joined UC Santa Barbara in 2018. Her group is interested in establishing materials design rules, and in optimizing materials processing approaches to advance electrochemical energy storage. The group's expertise lies in the development of magnetic resonance techniques, with an emphasis on real-time, operando analysis.

The Clément group has recently been recognized with an NSF CAREER Award (2022), a Camille Dreyfus Teacher-Scholar Award (2024), the IBA Early Career Researcher Award from the International Battery Association (2024), the Battery Division Early Career Award from the Electrochemical Society (2024), and the RSC Journal of Materials Chemistry Lectureship (2024).

For more information, please contact Jennifer Blankenship by email at jennifer@caltech.edu.