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Calcium Carbonate Formation in the Presence of Biopolymeric Additives
Published on: May 14, 2019
Revisiting Carbonate Additives through Dynamic Regulation of Cathode Electric Double Layers
Qi Yu1, Kaixiang Ren1, Xinchun Song1
1School of Materials Science and Engineering, Anhui University of Technology, Maanshan243002, China.
None:
Carbonate additives such as vinylene carbonate (VC) and fluoroethylene carbonate (FEC) are widely used to stabilize high-voltage lithium metal batteries (LMBs), but their roles are generally interpreted through a static film-forming mechanism. Here, we reassess their functions at LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes up to 4.6 V using in-situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS), theoretical calculations, and systematic electrochemical evaluation. VC and FEC not only contribute to cathode electrolyte interphase formation but also dynamically regulate the cathode-side electric double layer (EDL). By reducing its potential sensitivity, they suppress potential-driven redistribution and excessive enrichment of carbonate solvents and PF6- near the highly oxidizing NCM811 surface, thereby limiting continuous electrolyte decomposition. Compared with VC, FEC provides more durable protection by forming a LiF-rich organic-inorganic hybrid interphase. These findings reveal a new EDL-regulation mechanism for conventional carbonate additives and are expected to provide guidance for electrolyte design in high-voltage LMBs.
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