Understanding electrochemical and chemical reactions at the electrode-electrolyte interface is of fundamental importance for the safety and cycle life of Li-ion batteries. Positive electrode materials such as layered transition metal oxides exhibit different degrees of chemical reactivity with commonly used carbonate-based electrolytes. Here we employed density functional theory methods to compare the energetics of four different chemical reactions between ethylene carbonate (EC) and layered (LixMO2) and rocksalt (MO) oxide surfaces. EC dissociation on layered oxides was found energetically more favorable than nucleophilic attack, electrophilic attack, and EC dissociation with oxygen extraction from the oxide surface. In addition, EC dissociation became energetically more favorable on the oxide surfaces with transition metal ions from left to right on the periodic table or by increasing transition metal valence in the oxides, where higher degree of EC dissociation was found as the Fermi level was lowered into the oxide O 2p band.

Giordano, L., Karayaylali, P., Yu, Y., Katayama, Y., Maglia, F., Lux, S., et al. (2017). Chemical Reactivity Descriptor for the Oxide-Electrolyte Interface in Li-Ion Batteries. THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 8(16), 3881-3887 [10.1021/acs.jpclett.7b01655].

Chemical Reactivity Descriptor for the Oxide-Electrolyte Interface in Li-Ion Batteries

L. Giordano
;
2017

Abstract

Understanding electrochemical and chemical reactions at the electrode-electrolyte interface is of fundamental importance for the safety and cycle life of Li-ion batteries. Positive electrode materials such as layered transition metal oxides exhibit different degrees of chemical reactivity with commonly used carbonate-based electrolytes. Here we employed density functional theory methods to compare the energetics of four different chemical reactions between ethylene carbonate (EC) and layered (LixMO2) and rocksalt (MO) oxide surfaces. EC dissociation on layered oxides was found energetically more favorable than nucleophilic attack, electrophilic attack, and EC dissociation with oxygen extraction from the oxide surface. In addition, EC dissociation became energetically more favorable on the oxide surfaces with transition metal ions from left to right on the periodic table or by increasing transition metal valence in the oxides, where higher degree of EC dissociation was found as the Fermi level was lowered into the oxide O 2p band.
Articolo in rivista - Articolo scientifico
electrode-electrolyte interface, Li-ion batteries, DFT;
English
2017
8
16
3881
3887
reserved
Giordano, L., Karayaylali, P., Yu, Y., Katayama, Y., Maglia, F., Lux, S., et al. (2017). Chemical Reactivity Descriptor for the Oxide-Electrolyte Interface in Li-Ion Batteries. THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 8(16), 3881-3887 [10.1021/acs.jpclett.7b01655].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/299066
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