The use of lithium (Li) metal anodes in solid-state batteries is a strong strategy as a next-generation battery technology for surpassing the energy density and safety of conventional Li-ion batteries. However, in practice, current solid-state electrolytes have been limited to realize Li metal batteries due to their insufficient electrochemical and mechanical properties. Here, we design a new class of elastomeric electrolytes having a 3D interconnected plastic-crystal phase within the elastomer matrix—plastic crystal-embedded elastomer electrolytes (PCEEs).¹ To elucidate the effects of structural changes in PCEEs on Li-ion transport property, mechanical elasticity, and electrochemical performance, we investigate various phase-separated structures of PCEEs by adjusting each phase’s volume ratio. Among these structures, we reveal that bicontinuous-structured PCEE, consisting of an equal volume ratio of elastomer to plastic-crystal phase, is well-balanced to develop the efficient ion-conducting, plastic-crystal pathways within a mechanically robust, cross-linked elastomer matrix. Hence, this optimal PCEE shows a combination of high ionic conductivity (>10^-3 S cm^-1) at ambient temperature, high Li-ion transference number (>0.70), and good mechanical resilience (elongation at break ≈ 300%). A full cell configured with the optimized PCEE, a limited Li source, and a high loading LiNi_0.83Mn_0.6Co_1.1O₂ cathode delivers a high energy density exceeding 430 Wh kg_{anode+cathode+electrolyte}^-1. Understanding the structure-property-electrochemical performance relationship of PCEE through structural control can form the basis of structure-controlled elastomeric electrolytes, holding substantial promise in various electrochemical energy storage systems.

References

1. Lee, M. J.; Han, J.; Lee, K.; Lee, Y. J.; Kim, B. G.; Jung, K.-N; Kim, B. J.; Lee, S. W. Elastomeric electrolytes for high-energy solid-state lithium batteries. Nature 2022, 601, 217-222.