Origin of Superior Li‐Ion Transport in Lamellar Lyotropic Liquid Crystals for Beyond‐Liquid Electrolytes

Abstract Rational design of satisfactory electrolytes is of critical importance for efficient and sustainable energy devices. Herein, lamellar‐nanostructured lyotropic liquid crystal (LLC) electrolytes showing beyond‐liquid performance are designed for lithium‐ion batteries (LIBs) by constructing desirable amphiphile/liquid interfaces for lithium ion (Li ⁺ ) desolvation and transport. The lamellar LLC electrolytes are simply prepared by self‐assembly of amphiphilic 1‐hexadecyl‐3‐methylimidazoliumtetrafluoroborate ([C ₁₆ Mim][BF ₄ ]) in conventional LiBF ₄ liquid electrolytes, which forms periodic [C ₁₆ Mim][BF ₄ ] nanolayers and liquid nanolayers. The interactions at the lamellar [C ₁₆ Mim][BF ₄ ]/liquid interfaces facilitate Li ⁺ desolvation for much higher transference numbers, and the lamellar interfaces provides ordered pathways for efficient transport of desolvated Li ⁺ . The Li ⁺ transport along lamellar [C ₁₆ Mim][BF ₄ ]/liquid interfaces in LLC electrolytes contributes 46% Li ⁺ conductivities, which enables Li ⁺ conductivities superior to those of liquid electrolytes. However, similar Li ⁺ transport is lost at 1‐hexadecyl‐3‐vinylimidazoliumtetrafluoroborate based lamellar LLC electrolytes because the high steric hindrance of rigid vinyl moieties. Original from Li ⁺ transport along lamellar [C ₁₆ Mim][BF ₄ ]/liquid interfaces, the LLC electrolytes show beyond‐liquid performance in both efficiency and stability for LIBs. The work here provides fundamental guidance in the rational design of versatile nanostructured electrolytes with beyond‐liquid performance for diverse energy devices.