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Surface and Bulk Stabilization of Silicon Anodes with Mixed-Multivalent Additives: Ca(TFSI)2 and Mg(TFSI)2

Journal Article · · ACS Applied Materials and Interfaces
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  1. Argonne National Laboratory (ANL), Argonne, IL (United States)
  2. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
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Here, silicon is drawing attention as the upcoming anode material for the next generation of lithium-ion batteries due to its higher capacity compared to commercial graphite. However, silicon anions formed during lithiation are highly reactive with binder and electrolyte components creating an unstable SEI layer and limiting the calendar life of silicon anodes. The reactivity of lithium silicide and the formation of an unstable SEI layer is mitigated by utilizing the use of a mixture of Ca and Mg multivalent cations as an electrolyte additive for Si anodes to improve their calendar life. The effect of mixed salts on the bulk and surface of silicon anodes was studied by multiple structural characterization techniques. Ca and Mg ions in the electrolyte formed relatively thermodynamically stable quaternary Li-Ca-Mg-Si Zintl phases in an in-situ fashion and more stable and denser SEI layer on the Si particles. These in turn protect silicon particles against side reactions with electrolytes in a coin cell. The full cell with the mixed cation electrolyte demonstrates enhanced calendar life performance with lower measured current and current leakage than that of the baseline electrolyte due to reduced side reactions. Electron Microscopy, HRXRD, and solid-state NMR results showed that electrodes with mixed cations tended to have less cracking on the electrode surface compared to Si electrodes with Gen2 + FEC and the presence of mixed cations enhances cation migration and formation of quaternary Zintl phases stabilizing bulk and forming a more stable SEI.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-06CH11357; AC05-76RL01830
OSTI ID:
2475137
Alternate ID(s):
OSTI ID: 2481423
Report Number(s):
PNNL-SA--193135
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 16 Vol. 16; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
Si anodes
calendar life
electrolyte additives
lithium-ion batteries
mixed-salt electrolyte