Extraordinarily Stable Aqueous Electrochromic Battery Based on Li₄Ti₅O₁₂ and Hybrid Al³⁺/Zn²⁺ Electrolyte

Aqueous electrochromic battery (ECB) is a multifunctional technology that shows great potential in various applications including energy-saving buildings and wearable batteries with visible energy levels. However, owing to the mismatch between traditional electrochromic materials and the electrolyte, aqueous ECBs generally exhibit poor cycling stability which bottlenecks their practical commercialization. Herein, we present an ultrastable electrochromic system composed of lithium titanate (Li₄Ti₅O₁₂, LTO) electrode and Al³⁺/Zn²⁺ hybrid electrolyte. The fully compatible system exhibits excellent redox reaction reversibility, thus leading to extremely high cycling stabilities in optical contrast (12 500 cycles with unnoticeable degradation) and energy storage (4000 cycles with 82.6% retention of capacity), superior electrochromic performances including high optical contrast (∼74.73%) and fast responses (4.35 s/7.65 s for bleaching/coloring), as well as excellent discharge areal capacity of 151.94 mAh m^-2. The extraordinary cycling stability can be attributed to the robust [TiO₆] octahedral frameworks which remain chemically active even upon the gradual substitution of Li⁺ with Al³⁺ in LTO over multiple operation cycles. The high-performance electrochromic system demonstrated here not only makes the commercialization of low-cost, high-safety aqueous-based electrochromic devices possible but also provides potential design guidance for LTO-related materials used in aqueous-based energy storage devices.