Revisiting Coulombic Efficiency Paradigm: Electrolyte Additive Design for Lithium Metal Batteries
Angewandte Chemie, vol. 138
Abstract
ABSTRACT Small‐dose electrolyte additives are widely used to enhance battery performance, yet rational additive selection for the stabilization of lithium metal (Li°) electrodes remains challenging. Coulombic efficiency (CE) measurements in asymmetric Li°||Cu° cells serve as critical evaluative metrics, but the resulting CE values often deviate from expectations based on additive structure alone. Herein, we delve into the design of fluorinated electrolyte additives by combining statistical analysis of Li°||Cu° cycling data with compositional characterization as well as atomistic and chemical simulations. Our results demonstrate that nonafluorobutanesulfonyl fluoride, as an electrolyte additive, induces only a marginal effect on the Aurbach CE values during short‐term cycling tests of Li°||Cu° cells. Intriguingly, during extended‐cycling, statistical analysis reveals that the same additive exhibits divergent effects in electrolyte families based on bis(trifluoromethanesulfonyl)imide (TFSI − ) and bis(fluorosulfonyl)imide (FSI − ) anions. These differences arise from the interplay between the film‐forming chemistry of the fluorinated additive and the active involvement of TFSI − and FSI − anions, which collectively modulate the chemical and electrochemical features of the resulting solid‐electrolyte interphases (SEI) on Li°. This work elucidates how additive functionality translates into interphase chemistry and provides a statistically robust framework for screening electrolyte additives for practical lithium metal batteries.
Authors 17
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Huazhong University of Science and Technology
Affiliation as printed
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan China
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Huazhong University of Science and Technology
Affiliation as printed
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan China
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Huazhong University of Science and Technology
Affiliation as printed
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan China
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Huazhong University of Science and Technology
Affiliation as printed
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan China
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Affiliation as printed
Chinese Academy of Sciences Beijing China
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Affiliation as printed
Chinese Academy of Sciences Beijing China
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Affiliation as printed
Chinese Academy of Sciences Beijing China
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Affiliation as printed
Chinese Academy of Sciences Beijing China
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Huazhong University of Science and Technology
Affiliation as printed
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan China
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Affiliation as printed
Centre for Cooperative Research on Alternative Energies (CIC energiGUNE) Basque Research and Technology Alliance (BRTA) Vitoria‐Gasteiz Spain
IKERBASQUE Ikerbasque, Basque Foundation for Science Bilbao Spain
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Affiliation as printed
Chinese Academy of Sciences Beijing China
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Gebrekidan Gebresilassie Eshetu Aachen Institute of Power Electronics and Electric Drives Center for Ageing Reliability and Lifetime Prediction of Electrochemical and Power Electronic Systems (CARL)
Mekelle University · RWTH Aachen University
Affiliation as printed
Department of Materials Science and Engineering, Mekelle Institute of Technology Mekelle University Mekelle Ethiopia
Institute of Power Electronics and Electric Drives (ISEA), Center for Ageing Reliability and Lifetime Prediction of Electrochemical and Power Electronic Systems (CARL) RWTH Aachen University Aachen Germany
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Egbert Figgemeier Aachen Institute of Power Electronics and Electric Drives Center for Ageing Reliability and Lifetime Prediction of Electrochemical and Power Electronic Systems (CARL)
Forschungszentrum Jülich · Helmholtz-Institute Münster · Jülich Aachen Research Alliance · RWTH Aachen University
Affiliation as printed
Helmholtz Institute Münster (HIMS), Institute of Energy Materials and Devices (IMD 4) Forschungszentrum Jülich GmbH Münster Germany
Institute of Power Electronics and Electric Drives (ISEA), Center for Ageing Reliability and Lifetime Prediction of Electrochemical and Power Electronic Systems (CARL) RWTH Aachen University Aachen Germany
Jülich Aachen Research Alliance JARA‐Energy Jülich Germany
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Affiliation as printed
Centre for Cooperative Research on Alternative Energies (CIC energiGUNE) Basque Research and Technology Alliance (BRTA) Vitoria‐Gasteiz Spain
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Affiliation as printed
Chinese Academy of Sciences Beijing China
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Huazhong University of Science and Technology
Affiliation as printed
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan China
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Huazhong University of Science and Technology
Affiliation as printed
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan China
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