Although monovalent lithium has been successfully used as a coloring ion in electrochromic applications, it still faces the challenges of low safety, high cost, and limited reserves. Herein, we demonstrate that the amorphous WO3 films intercalated with Al3+ ions could exhibit desired wide optical modulation (∼63.0%) and high coloration efficiency (∼72.0 cm2 A–1, which is >100% higher than that with Li+ or Na+), benefiting from the three-electron redox properties of aluminum. Due to the strong electrostatic force and large atomic weight, the charge exchange processes for Al3+ ions are limited only to the near-surface region and consequently bring about enhanced electrochromic stability. Our findings provide in-depth insights into the nature of electrochromism and also open up a new route toward scalable electrochromic devices using sputtering techniques and earth-abundant materials.

With large interstitial space volumes and fast ion diffusion pathways, amorphous metal oxides as cathodic intercalation materials for electrochromic devices have attracted attention. However, these incompact thin films normally suffer from two inevitable imperfections: self-deintercalation of guest ions and poor stability of the structure, which constitute a big obstacle toward the development of high-stable commercial applications. Here, we present a low-cost, eco-friendly hybrid cation 1,2-PG-AlCl3·6H2O electrolyte, in which the sputter-deposited a-WO3–x thin film can exhibit both the long-desired excellent open-circuit memory (>100 h, with zero optical loss) and super-long cycling lifetime (∼20,000 cycles, with 80% optical modulation), benefiting from the formation of unique Al-hydroxide-based solid electrolyte interphase during electrochromic operations. In addition, the optical absorption behaviors in a-WO3–x caused by host–guest interactions were elaborated. We demonstrated that the intervalence transfers are primarily via the “corner-sharing” related path (W5+ ↔ W6+) but not the “edge-sharing” related paths (W4+ ↔ W6+ and/or W4+ ↔ W5+), and the small polaron/electron transfers taking place at the W–O bond-breaking positions are not allowed. Our findings might provide in-depth insights into the nature of electrochromism and provide a significant step in the realization of more stable, more excellent electrochromic applications based on amorphous metal oxides.

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