Porous materials for lithium-sulfur batteries - mechanochemical synthesis and performance probed by in situ and operando techniques (2024)
- Authors:
- Autor USP: SOUZA, BRENO LUIZ DE - IQ
- Unidade: IQ
- DOI: 10.11606/T.46.2024.tde-27052025-174352
- Subjects: ELETROQUÍMICA; LÍTIO; ENXOFRE; ESPECTROSCOPIA
- Keywords: Bateria de Lítio-Enxofre; Electrochemistry; Eletroquímica; Impedance; Impedância; in situ and operando X-Rays; in situ e operando X-Rays; Lithium-Sulfur Battery; Mecanoquímica; Mechanochemistry
- Agências de fomento:
- Language: Inglês
- Abstract: Lithium-Sulfur Batteries (LiSBs) represent a promising solution for nextgeneration energy storage, boasting an exceptional theoretical capacity of 1675 mA h g-¹, a feat nearly five times higher than traditional transition metal oxides and phosphates. The 16-electron transfer during the de/lithiation process at a working voltage of ~1.7-3.0 V vs Li+/Li enables a theoretical density of 2600 Wh Kg-¹. However, the substantial challenges faced by LiSBs, primarily rapid capacity fading due to sulfur electrode pulverization and the shuttle effect caused by the dissolution of long-chain polysulfides (LiPSs) in organic solvents, have prompted extensive investigation. This work systematically addresses these challenges through the synthesis and characterization of diverse porous compounds, each detailed in the following chapters. Chapter 2 introduces a novel mechanochemical approach for crafting Zeolitic Imidazole Framework ZIF-8-based composites as sulfur hosts in positive electrodes for LiSBs. Exploring various techniques for integrating conductive carbon and substituting Zn²+ with other bivalent metals (Cu²+, Co²+, and Ni²+), alternative ZIF-8-derived materials are obtained. The ZIF-8/C/S₈ positive electrode, Mechanochemically Mixed, showcases a remarkable 54% performance improvement over traditional ZIF-8/S₈ slurry preparation, underscoring the advantages of direct mechanochemical synthesis during the initial charge/discharge cycles. Chapter 3 focuses on a 3D polypyrrole-based sponge (PPY) synthesized as a sulfur host for positive electrodes in LiSBs. Optimized PPY:S8 exhibits compelling electrochemical performance, including a cycle lifetime exceeding 200 cycles. Electrochemical impedance spectroscopy (EIS) indicates a minimal shuttle effect through an unchanged solution resistance, and operando Raman spectroscopy reveals the stability of the bipolaronic state and the "neutralization" of LiPSs.These findings underscore PPY's potential as an effective sulfur host, mitigating the shuttle effect and enhancing the charge storage capacity of LiSBs. Chapter 4 delves into understanding degradation mechanisms within LiSBs, focusing on a porous organic polymer (POP), MTP-1. Synthesized using eco-friendly methods (mechanochemistry), MTP-1 is thoroughly characterized, exhibiting robust performance with over 70% capacity retention across 100 cycles. Operando techniques, including electrochemical impedance spectroscopy (EIS) and X-ray radiography (in lab and Synchrotron), reveal superior sulfur confinement and stability. The synergy of environmentally friendly synthesis, extensive characterization, and advanced in situ and operando techniques positions MTP-1 as a promising sulfur host material. Overall, these diverse approaches collectively underscore the significance of tailored materials and advanced techniques in overcoming LiSBs challenges. Each chapter contributes valuable insights, collectively advancing LiSBs technology and our understanding of degradation mechanisms. This work holds promise for the widespread implementation of LiSBs, addressing critical issues and contributing to the development of advanced materials for energy storage systems.
- Imprenta:
- Data da defesa: 23.01.2024
- Este periódico é de acesso aberto
- Este artigo é de acesso aberto
- URL de acesso aberto
- Cor do Acesso Aberto: gold
- Licença: cc-by-nc-sa
-
ABNT
SOUZA, Breno Luiz de. Porous materials for lithium-sulfur batteries - mechanochemical synthesis and performance probed by in situ and operando techniques. 2024. Tese (Doutorado) – Universidade de São Paulo, São Paulo, 2024. Disponível em: https://www.teses.usp.br/teses/disponiveis/46/46136/tde-27052025-174352/. Acesso em: 27 dez. 2025. -
APA
Souza, B. L. de. (2024). Porous materials for lithium-sulfur batteries - mechanochemical synthesis and performance probed by in situ and operando techniques (Tese (Doutorado). Universidade de São Paulo, São Paulo. Recuperado de https://www.teses.usp.br/teses/disponiveis/46/46136/tde-27052025-174352/ -
NLM
Souza BL de. Porous materials for lithium-sulfur batteries - mechanochemical synthesis and performance probed by in situ and operando techniques [Internet]. 2024 ;[citado 2025 dez. 27 ] Available from: https://www.teses.usp.br/teses/disponiveis/46/46136/tde-27052025-174352/ -
Vancouver
Souza BL de. Porous materials for lithium-sulfur batteries - mechanochemical synthesis and performance probed by in situ and operando techniques [Internet]. 2024 ;[citado 2025 dez. 27 ] Available from: https://www.teses.usp.br/teses/disponiveis/46/46136/tde-27052025-174352/ - Covalent-sulfur polymer positive electrode for enhanced stability in lithium-sulfur batteries
- Zeolitic imidazole framework-based materials by mechanochemical synthesis applied as positive electrodes in lithium sulfur batteries
- Investigating porous electrode systems in lithium/sulfur batteries by in-situ and operando techniques
- WiSE as a solution to challenges in zinc-air batteries
- Unveiling the lithium-sulfur batteries: insights from a multidimensional in-situ and operando cell
- Unveiling the polysulfide-PPY interaction for enhanced lithium–sulfur battery performance
- Tackling lithium-sulfur battery challenges with porous materials and operando techniques
- Mechanochemical optimization of ZIF-8/Carbon/S8 composites for lithium-sulfur batteries positive electrodes
- Sulfur-rich covalent polymer for enhanced cycling in Li-S batteries
- Mechanochemical hydroquinone regeneration promotes gold salt reduction in sub-stoichiometric conditions of the reducing agent
Informações sobre o DOI: 10.11606/T.46.2024.tde-27052025-174352 (Fonte: oaDOI API)
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