Organic-Inorganic-Induced Polymer Intercalation into Layered Composites for Aqueous Zinc-Ion Battery

Abstract

Rechargeable aqueous zinc-based batteries are very attractive alternative devices for current energy storage by virtue of their low cost and high security. However, the performance of vanadium oxide cathode strongly relies on the distance of interlayer spacing. Here, we employ layered PEDOT-NH 4 V 3 O 8 (PEDOT-NVO) as a cathode material, which produces an enlarged interlayer spacing of 10.8 Å (against 7.8 Å for the single NVO) by effectively conducting polymer intercalation. This cathode material exhibits an improved capacity of 356.8 mAh g À1 at 0.05 A g À1 and 163.6 mAh g À1 , even at the highest current density of 10 A g À1 (with a high retention from 0.05 to 10 A g À1 ), and features an ultra-long lifetime of over 5,000 charge-discharge cycles with a capacity retention of 94.1%. A combination of mechanism analyses and theoretical calculations suggest that the oxygen vacancies and larger interlayer spacing through polymer assistance account for the improved electrochemical performance.

Design Strategies for High‐Performance Aqueous Zn/Organic Batteries

“…[52][53][54][55][56] They often display bipolar-type redox chemistry in aqueous ZIBs.Inthe case of Zn/PANI batteries, Zn 2+ could serve as the cation species associated with the imine-related redox reaction, while the counter anions will participate in the reaction between the =NH + -a nd -NHmoieties during charge/discharge processes.A lthough they often deliver limited specific capacity (< 200 mAh g À1 )due to their low available doping level, they usually display more stable electrochemical performance in comparison with other most previous reported cathode materials.A saresult, they were usually utilized to act as the electrodes of flexible ZIBs with various configurations. [57][58][59][60][61][62] Thee lectrochemical performance of conductive polymers could be further improved by the optimization of electrolyte, [27,63] hybridization with inorganic materials, [28,[64][65][66][67] morphology regulation [68] and copolymerization. [38,[69][70][71] Forinstance,the conductive polymers could be intercalated into the interlayers of metal oxides to effectively eliminate the structural changes of them during discharge/charge processes,r esulting in excellent rate capability and long cycling life.…”

Interlayer Doping in Layered Vanadium Oxides for Low‐cost Energy Storage: Sodium‐ion Batteries and Aqueous Zinc‐ion Batteries

“…According to the XPS analysis by Bin et al. (Figure 5b), the expanded d ‐spacing of NH 4 V 3 O 8 by pre‐intercalated organic molecules can significantly increase the accommodated ions and thus activate V 5+ /V 3+ pair (Figure 5c) [64] . Meanwhile, the carbonization characteristics of organic materials could also be helpful in forming the layer‐by‐layer structure similar to “superlattice” at high temperature [65] .…”

“…(b) High‐resolution XPS spectra of V 2p when discharged to 0.4 V. (c) The second cycle of CV curves and charge‐discharge profiles. Reprinted with permission from Bin et al [64] . Copyright 2020 Elsevier Inc. (d) Reduced electrostatic interaction of polyaniline pre‐intercalated V 2 O 5 .…”

NMR Study of Intercalates and Grafted Organic Derivatives of H2La2Ti3O10

“…The properties of hybrid materials are governed beside others by the type of chemical bonding between the organic and inorganic parts. Intercalated hybrids not only combine the physicochemical properties of both inorganic and organic parts but may exhibit synergetic behaviors afforded by both moieties, making possible the development of novel physicochemical devices [ 35 , 36 ]. Moreover, they can be used as an intermediate step for the synthesis of covalent hydrides [ 37 ].…”