Design of Highly Efficient Catalysts and Advanced Electrodes for High-Performance Aqueous Zn-S Batteries
| dc.contributor.advisor | Qiao, Shizhang | |
| dc.contributor.advisor | Ye, Chao | |
| dc.contributor.author | Liu, Jiahao | |
| dc.contributor.school | School of Chemical Engineering | |
| dc.date.issued | 2025 | |
| dc.description.abstract | The growing demand for efficient and sustainable energy storage systems has driven the exploration of alternatives to conventional lithium-ion batteries, which are limited by high costs, safety risks, and scalability challenges. Aqueous zinc-sulfur batteries have emerged as a highly promising candidate, offering exceptional theoretical capacity (1675 mAh g−1 for sulfur and 820 mAh g−1 for Zn), cost-effectiveness (52 Ah $−1), and environmental compatibility. Nevertheless, AZSBs face significant challenges, including severe cathode and anode polarizations, an unclear electrochemical rate-determining step, low Coulombic efficiency, and inferior practical energy density. These challenges impede their practical deployment in highperformance energy storage systems. This thesis addresses these challenges through a comprehensive approach, focusing on the design of highly efficient catalysts with both liquid and solid phases, as well as the development of advanced electrodes for robust anode interfaces and high sulfur-loading cathodes. By systematically enhancing AZSBs from catalysts to electrodes, this work strives to realize their full potential for next-generation energy storage solutions. Firstly, we developed a two-dimensional mesoporous zincophilic sieve (2DZS) as a kinetic anode interface to address the polarization issue in AZSBs. The 2DZS interface features zincophilic sites and hydrophobic properties, which enhance Zn2+ diffusion kinetics and suppress hydrogen evolution and dendrite growth. This design significantly reduces anodic polarization and improves the energy density and cycling stability of SZBs, achieving a high energy density of 866 Wh kg–1 based on sulfur mass and a lifespan of 10,000 cycles at 8 A g–1. Secondly, we designed high-entropy sulfide (HES) catalysts to address the sluggish cathode kinetics of the solid-solid Zn-S redox process in AZSBs. The HES catalysts accelerate the rate-determining step conversion of ZnS2 to wurtzite ZnS, improving sulfur utilization and suppressing by-product formation. Additionally, the HES catalysts mitigate transition metal leaching and water splitting, enhancing cycling stability. As a result, the pouch cell with HES catalysts achieve over 400 cycles at 4 C with a capacity decay of only 0.06% per cycle, demonstrating a promising strategy for stable and fast-charging metal-sulfur batteries. Thirdly, we introduced a covalent iodo-thiadiazole anti-corrosive redox mediator (CIM) as a liquid catalyst to address the low CE in aqueous AZSBs. The CIM catalyst suppresses I3−- mediated anode corrosion through its covalent C–I bond on position 5 in the thiadiazole ring (C5–I) and enhances cathode kinetics via a dynamic electronic restructuring effect. This dualfunction mechanism enables CIM-based AZSBs to achieve an average CE of ~99.68% and maintain 98.8% capacity retention over 700 cycles at 20 A g−1. Additionally, CIM-based pouch cells deliver a high capacity of 1393 mAh g−1 after 120 cycles at 2 A g−1, demonstrating a promising strategy for high-CE aqueous metal-sulfur batteries. Finally, we developed a high sulfur loading (8-12 mg cm–2) cathode and a hierarchical bromine-thiourea (BTU) mediator to realize the practical pouch AZSBs. The BTU mediator combines thiourea’s corrosion resistance with ZnBr2’s catalytic activity, eliminating Brinduced corrosion, accelerating Zn-S redox kinetics, and mitigating "dead ZnS" formation. This strategy enables the assembled pouch cell to achieve a record discharge capacity of 1610 mAh g−1 at 0.71 V. The pouch cell delivers an ultra-stable cycling performance of 1,000 cycles at 6.7 A g−1, with a high energy density of 761 Wh kg−1 base on cathode mass. It sets a new benchmark for pouch AZSBs and providing a universal approach to enhance sulfur loading in aqueous pouch metal-sulfur batteries. | |
| dc.description.dissertation | Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering. 2025 | en |
| dc.identifier.uri | https://hdl.handle.net/2440/146182 | |
| dc.language.iso | en | |
| dc.provenance | This electronic version is made publicly available by the University of Adelaide in accordance with its open access policy for student theses. Copyright in this thesis remains with the author. This thesis may incorporate third party material which has been used by the author pursuant to Fair Dealing exceptions. If you are the owner of any included third party copyright material you wish to be removed from this electronic version, please complete the take down form located at: http://www.adelaide.edu.au/legals | en |
| dc.subject | Aqueous Zn-S batteries | |
| dc.subject | 2D mesoporous interfaces | |
| dc.subject | high-entropy catalysts | |
| dc.subject | redox mediators | |
| dc.title | Design of Highly Efficient Catalysts and Advanced Electrodes for High-Performance Aqueous Zn-S Batteries | |
| dc.type | Thesis | en |
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