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Title: Redox-active zinc thiolates for low-cost aqueous rechargeable Zn-ion batteries
Aqueous zinc-ion batteries (AZIBs) are promising candidates for large-scale electrical energy storage due to the inexpensive, safe, and non-toxic nature of zinc. One key area that requires further development is electrode materials that store Zn 2+ ions with high reversibility and fast kinetics. To determine the viability of low-cost organosulfur compounds as OEMs for AZIBs, we investigate how structural modification affects electrochemical performance in Zn-thiolate complexes 1 and 2. Remarkably, modification of one thiolate in 1 to sulfide in 2 reduces the voltage hysteresis from 1.04 V to 0.15 V. While 1 exhibits negligible specific capacity due to the formation of insulating DMcT polymers, 2 delivers a capacity of 107 mA h g −1 with a primary discharge plateau at 1.1 V vs. Zn 2+ /Zn. Spectroscopic studies of 2 suggest a Zn 2+ and H + co-insertion mechanism with Zn 2+ as the predominant charge carrier. Capacity fading in Zn-2 cells likely results from the formation of (i) soluble H + insertion products and (ii) non-redox-active side products. Increasing electrolyte concentration and using a Nafion membrane significantly enhances the stability of 2 by suppressing H + insertion. Our findings provide insight into the molecular design strategies to reduce the polarization potential and improve the cycling stability of the thiolate/disulfide redox couple in aqueous battery systems.  more » « less
Award ID(s):
2124604 2011876
PAR ID:
10348184
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Chemical Science
Volume:
12
Issue:
46
ISSN:
2041-6520
Page Range / eLocation ID:
15253 to 15262
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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