Abstract
Zn-ion hybrid supercapacitors (ZHCs) combining merits of battery-type and capacitive electrodes are considered to be a prospective candidate in energy storage systems. Tailor-made carbon cathodes with high zincophilicity and abundant physi/chemisorption sites are critical but it remains a great challenge to achieve both features by a sustainable means. Herein, a hydrogen-bonding interaction-guided self-assembly strategy is presented to prepare iodine-doped carbon nanocages without templates for boosting zinc-ion storage by nucleophilicity. The biomass ellagic acid contains extensional hydroxy and acyloxy groups with electron-donating ability, which interact with melamine and ammonium iodide to form organic supermolecules. The organic supermolecules further self-assemble into a nanocage-like structure with cavities under hydrothermal processes via hydrogen-bonding and π-π stacking. The carbon nanocages as ZHCs cathodes enable the high approachability of zincophilic sites and low ion migration resistance resulting from the interconnected conductive network and nanoscale architecture. The experimental analyses and theoretical simulations reveal the pivotal role of iodine dopants. The I(5)(-)/I(3)(-) doping anions in carbon cathodes have a nucleophilicity to preferentially adsorb the Zn(2+) cation by the formation of C(+)-I(5)(-)-Zn(2+) and C(+)-I(3)(-)-Zn(2+). Of these, the C(+)-I(3)(-) shows stronger bonding with Zn(2+) than C(+)-I(5)(-). As a result, the iodine-doped carbon nanocages produced via this template-free strategy deliver a high capacity of 134.2 mAh/g at 1 A/g and a maximum energy and power density of 114.1 Wh/kg and 42.5 kW/kg.