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Molecular-Level Insights into the Reactivity of Siloxane-Based Electrolytes at a Lithium-Metal Anode

Journal Article · · ChemPhysChem
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Molecular level understanding of the reactions that occur at the lithium metal anode/electrolyte interphase is essential to improve the performance of Li-O2 batteries. Experimental and computational techniques were utilized to explore the reactivity of tri(ethylene glycol)-substituted trimethylsilane (1NM3), a siloxane based ether electrolyte, at the lithium metal anode. In situ/ex situ XRD and FTIR measurements provide evidence for the formation of lithium hydroxide and lithium carbonates at the anode upon gradual degradation of the metallic lithium anode and the solvent molecules in the presence of oxygen. Density functional calculations performed to obtain mechanistic understanding of the reductive decomposition of 1NM3 indicate that the decomposition does not require any apparent barrier to produce lithium hydroxide and lithium carbonates when the reduced 1NM3 solvent molecules interact with the oxygen crossing over from the cathode. This study indicates that the degradation of the 1NM3 solvent may be more than the linear ethers such as tetraglyme or dioxalone due to its relatively higher electron affinity. Also, this study indicates that the protection of lithium metal and prevention of oxygen crossover to the anode is essential to minimize electrolyte and anode decomposition.
Research Organization:
Argonne National Laboratory (ANL)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technology; USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division
DOE Contract Number:
AC02-06CH11357
OSTI ID:
1396296
Journal Information:
ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 10 Vol. 15; ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English

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