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Nanomaterials, Vol. 9, Pages 1664: Studies on Possible Ion-Confinement in Nanopore for Enhanced Supercapacitor Performance in 4V EMIBF4 Ionic Liquids

Research paper by Jie Deng, Jing Li, Zhe Xiao, Shuang Song, Luming Li

Indexed on: 25 Nov '19Published on: 22 Nov '19Published in: Nanomaterials (Basel, Switzerland)



Abstract

Supercapacitors have the rapid charge/discharge kinetics and long stability in comparison with various batteries yet undergo low energy density. Theoretically, square dependence of energy density upon voltage reveals a fruitful but challenging engineering tenet to address this long-standing problem by keeping a large voltage window in the compositionally/structurally fine-tuned electrode/electrolyte systems. Inspired by this, a facile salt-templating enables hierarchically porous biochars for supercapacitors filled by the high-voltage ionic liquids (ILs). Resultant nanostructures possess a coherent/interpenetrated framework of curved atom-thick sidewalls of 0.8-/1.5-nanometer pores to reconcile the pore-size-dependent adlayer structures of ILs in nanopores. Surprisingly, this narrow dual-model pore matches ionic radii of selected ILs to accommodate ions by unique coupled nano-/bi-layer nanoconfinements, augmenting the degree of confinement (DoC). The high DoC efficiently undermines the coulombic ordering networks and induces the local conformational oscillations, thus triggering an anomalous but robust charge separation. This novel bi-/mono-layer nanoconfinement combination mediates harmful overscreening/overcrowding effects to reinforce ion-partitioning, mitigating long-lasting conflicts of power/energy densities. This interesting result differs from a long-held viewpoint regarding the sieving effect that ion-in-pore capacitance peaks only if pore size critically approaches the ion dimension. Optimal biocarbon finally presents a very high/stable operational voltage up to 4 V and specific energy/power rating (88.3 Whkg−1 at 1 kWkg−1, 47.7 Whkg−1 albeit at a high battery-accessible specific power density of 20 kWkg−1), overwhelmingly outperforming most hitherto-reported supercapacitors and some batteries. Such attractive charge storage level can preliminarily elucidate an alternative form of a super-ionic-state high-energy storage linked with both the coordination number and coulombic periodism of the few ion-sized mesopores inside carbon electrodes, escalating supercapacitors into a novel criterion of charge delivery.