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.
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A Study on the Synthesis and Proton Transport Behavior of Multilayered ZSM-5 Zeolite Nanosheet Membranes Laminated on Polymer Substrates
Single crystalline ZSM-5 ZNs with thicknesses around 6 nm were obtained by secondary growth of silicalite nanoparticles using diquaternary bis-1,5(tripropyl ammonium) pentamethylene diiodide (dC5) as a structure-directing agent (SDA). The dC5 could be effectively removed from the ZN pores by either high-temperature calcination or UV irradiation in air at room temperature but not by the piranha solution treatment. Ultrathin ZN-laminated membranes (ZNLMs) were fabricated by sandwiching a UV-activated multilayered ZN film between two recast Nafion® layers (ZNLM-Nafion) and by filtration coating from a suspension of thermally activated ZNs on a nonionic porous PVDF (ZNLM-PVDF). The ZNLMs on both supports demonstrated the ability of highly proton-selective ion conduction with low resistances in aqueous electrolyte solutions. The ZNLM-PVDF with PVDF binder was structurally stable, and it achieved a comparably low ASR but much higher proton selectivity compared with a Nafion membrane of same overall thickness. However, detachment between the ZNLM and Nafion layers occurred when the ZNLM-Nafion operated in aqueous electrolyte solutions. Results of this study show the potential for developing ZNLMs as efficient proton-conducting membranes without using expensive ionic polymer matrices. However, the development of polymer-supported ZNLMs is hindered by the current inefficiency in preparing well-dispersed suspensions of open-pore ZNs. Future development of efficient methods for synthesizing open-pore ZNs in dispersed states is key to realizing high-performance ZNLMs on polymers.
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- Award ID(s):
- 1935205
- PAR ID:
- 10463751
- Date Published:
- Journal Name:
- Membranes
- Volume:
- 13
- Issue:
- 3
- ISSN:
- 2077-0375
- Page Range / eLocation ID:
- 305
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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