001044912 001__ 1044912 001044912 005__ 20251127202202.0 001044912 0247_ $$2doi$$a10.1002/batt.202400568 001044912 0247_ $$2datacite_doi$$a10.34734/FZJ-2025-03434 001044912 037__ $$aFZJ-2025-03434 001044912 082__ $$a540 001044912 1001_ $$0P:(DE-Juel1)190810$$aWeiling, Matthias$$b0 001044912 245__ $$aComprehensive Study on Cell Components in High‐Voltage Pouch Cells with Lithium Perchlorate: Decomposition, Transesterification, Chlorination, Deposition, and Self‐Discharge 001044912 260__ $$aWeinheim$$bWiley-VCH$$c2025 001044912 3367_ $$2DRIVER$$aarticle 001044912 3367_ $$2DataCite$$aOutput Types/Journal article 001044912 3367_ $$0PUB:(DE-HGF)16$$2PUB:(DE-HGF)$$aJournal Article$$bjournal$$mjournal$$s1764230173_28328 001044912 3367_ $$2BibTeX$$aARTICLE 001044912 3367_ $$2ORCID$$aJOURNAL_ARTICLE 001044912 3367_ $$00$$2EndNote$$aJournal Article 001044912 520__ $$aBattery development has traditionally focused on high energy and long lifetime cells, but there is now a shift towards their sustainability and safety. One example of this trend is the search for fluorine-free conductive salts. The overwhelming majority of lithium-ion conductive salts contain fluorine, which is critical regarding their environmental impact, sustainability, and toxicology. In this study, we perform a comprehensive investigation of the performance and aging mechanisms of cell components with LiClO4 as conductive salt in high-voltage NMC622‖Graphite pouch cells. The cells containing LiClO4 show poorer electrochemical performance compared to their LiPF6 equivalents. However, to the best of our knowledge, a mechanistic understanding of the effect of LiClO4 on the aging of electrode and electrolyte components for high-voltage cells is largely missing. Developing such an understanding will pave the way toward designing alternative salts to LiPF6, ultimately leading to fluorine-free and more sustainable battery cells. Our results show, that the chlorination of ethyl methyl carbonate at both methyl and ethyl groups and the formation of large (Liw)AlxOyClz composite deposits on the cathode surface result from perchlorate degradation at the cathode. 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