Tuning Ionic Conductivity in High Entropy Lithium Argyrodite Solid Electrolytes

Florian Strauss^a, Shango Li^b, Jing Lin^a, Mareen Schaller^c, Sylvio Indris^c, Xin Zhang^b, Torsten Brezesinski^a, Ce-Wen Nan^d, Shuo Wang^b

^aInstitute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

^bbCenter of Smart Materials and Devices, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing & School of Material Science and Engineering, Wuhan University of Technology

^cInstitute of Applied Materials and Institute of Nanotechnoloy, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany

^dState Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University

Proceedings of 24th International Conference on Solid State Ionics (SSI24)

Emerging Materials for High-Performance Devices

London, United Kingdom, 2024 July 14th - 19th

Organizers: John Kilner and Stephen Skinner

Oral, Florian Strauss, presentation 412
Publication date: 10th April 2024

Solid-state batteries (SSBs) are attracting great interest leading to potentially higher energy and power densities compared conventional Li-ion batteries based on liquid electrolytes. However, they are plagued by the development of advanced solid electrolytes (SEs), mainly lacking in ionic conductivity and electrochemical stability; thus, the ongoing quest for exploration of new materials and compositions.

Inducing a large structural disorder, i.e. high configurational entropy, has recently emerged as a new strategy to overcome limitations of conventional SE materials. In this regard, few multicomponent SE materials have been reported up to now, showing favorable charge-transport properties [1,2]. However, a thorough understanding on how configurational entropy (ΔS_conf) affects ionic conductivity is lacking. Here, we successfully synthesized a solid solution series of halogen-rich lithium argyrodites with the general formula Li_5.5PS_4.5Cl_xBr_1.5−x (0 ≤ x ≤ 1.5) [3]. Using neutron powder diffraction and ³¹P magic-angle spinning nuclear magnetic resonance spectroscopy, the shared S²⁻/Cl⁻/Br⁻ occupancy on the anion sublattice was quantitatively analyzed. We show that anion disorder positively affects Li-ion dynamics, leading to a room-temperature ionic conductivity of 22.7 mS cm⁻¹ (9.6 mS cm⁻¹ in cold-pressed state) for Li_5.5PS_4.5Cl_0.8Br_0.7 (ΔS_conf= 1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li_5.5PS_4.5Cl_0.8Br_0.7 SE allowed for stable cycling of single-crystal LiNi_0.9Co_0.06Mn_0.04O₂ (s-NCM90) composite cathodes in SSB cells, emphasizing that dual-substituted lithium argyrodites hold great promise in enabling high-performance electrochemical energy storage.

References:

[1] Lin, J.; Charkashinin, G.; Schäfer, M.; Melinte, Georgian.; Kndris, S.; Kondrakov, A.; Janek, J.; Brezesinski, T.; Strauss, F. A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte.ACS Material Letters 2022, 11, 2187-2194.

[2] Li, Y.; Song, S.; Kim, H.; Nomoto, K.; Kim, H.; Sun, X.; Hori, S.; Suzuki, K.; Matsui, N.; Hirayama, M.; Mizoguchi, G.; Saito, T.; Kamiyama, T.; Kanno, R. A lithium superionic conductor for millimeter-thick battery electrode. Science 2023, 381, 50-53.

[3] Li, S.; Lin, J.; Schaller, M.; Indris, S.; Zhang, Z.; Brezesinski, T.; Nan, C.-W.; Wang, S.; Strauss, F. High-Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All-Solid-State Batteries. Angew. Chem. 2023, 62, e2023141.

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