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Ethylene carbonate decomposition on pristine and oxygen-deficient binary metal oxide surfaces of battery cathode coating.

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Title: Ethylene carbonate decomposition on pristine and oxygen-deficient binary metal oxide surfaces of battery cathode coating.
Authors: Rendy, Bernardus1 (AUTHOR), Shukri, Ganes1,2 (AUTHOR), Mahyuddin, Muhammad Haris1,2 (AUTHOR), Akbar, Fiki Taufik3 (AUTHOR), Dipojono, Hermawan Kresno1,2 (AUTHOR), Rusydi, Febdian1,4,5 (AUTHOR) rusydi@fst.unair.ac.id, Saputro, Adhitya Gandaryus1,2 (AUTHOR) gandaryus@itb.ac.id
Source: Materials Chemistry & Physics. Jan2026:Part 1, Vol. 348, pN.PAG-N.PAG. 1p.
Subjects: Lithium-ion batteries, Density functional theory, Mathematical decomposition, Thermodynamics, Ethylene carbonates, Metallic oxides, Cathodes
Abstract: To control cathode-electrolyte side reactions and improve the performance of lithium-ion batteries (LIBs), understanding factors affecting the electrolyte component reactivities on binary metal oxides (BMOs) cathode coatings is essential. While such reactions on cathode surfaces have been studied intensively, that is not the case for BMOs cathode coating surfaces. Herein, we use density functional theory (DFT) calculations to quantitatively compare the thermodynamic driving forces of the commercial liquid electrolyte ethylene carbonate (EC) ring-opening catalytic decomposition on the pristine and oxygen-deficient surfaces of four representative BMO's viz. ▪ , MgO, ▪ , and ▪. We find that EC decomposition on both pristine and oxygen-deficient BMOs surfaces thermodynamically favors the formation of ▪ and ▪ gasses and products such as (adsorbed) hydrogen atom (▪), ▪ , ▪ , and ▪. Comparison with EC decomposition energies on bare layered-oxide based cathodes of LIBs (viz. LiCoO 2 , LiNiO 2 and LiMn 2 O 4) however show that the ▪ and ▪ have lesser thermodynamic driving force to catalytically decompose EC even in their O-deficient state (< −1.2 eV). In contrast, O-deficient MgO and ▪ have similar (or even stronger) EC decomposition reaction enthalpies of EC than that on the layered-oxide based cathodes (-̃2.0 eV). Our results point out that point defect such as oxygen vacancy O v a c in BMOs, which in most cases are inherently present within the BMOs, induces different reactivity measure on the EC decomposition reaction. Finally, we further point out that the enthalpy of ▪ adsorption on oxygen-deficient surfaces coupled with the O v a c formation energy may serve as practical parameters for designing an effective BMO-based LIB cathode coating material. [Display omitted] • Adsorption and decomposition of ethylene carbonate on metal oxide surfaces. • The decompositions are mostly exothermic relative to the adsorbed state. • The decomposition products are CO 2 , C 2 H 4 , H*, CH 3 CHO*, CH 2 CHO*, and CH 2 CHOCOO*. • The decompositions indirectly contribute to capacity reduction and cell pressure. • Factors affecting the decomposition thermodynamic driving force are discussed. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:To control cathode-electrolyte side reactions and improve the performance of lithium-ion batteries (LIBs), understanding factors affecting the electrolyte component reactivities on binary metal oxides (BMOs) cathode coatings is essential. While such reactions on cathode surfaces have been studied intensively, that is not the case for BMOs cathode coating surfaces. Herein, we use density functional theory (DFT) calculations to quantitatively compare the thermodynamic driving forces of the commercial liquid electrolyte ethylene carbonate (EC) ring-opening catalytic decomposition on the pristine and oxygen-deficient surfaces of four representative BMO's viz. ▪ , MgO, ▪ , and ▪. We find that EC decomposition on both pristine and oxygen-deficient BMOs surfaces thermodynamically favors the formation of ▪ and ▪ gasses and products such as (adsorbed) hydrogen atom (▪), ▪ , ▪ , and ▪. Comparison with EC decomposition energies on bare layered-oxide based cathodes of LIBs (viz. LiCoO 2 , LiNiO 2 and LiMn 2 O 4) however show that the ▪ and ▪ have lesser thermodynamic driving force to catalytically decompose EC even in their O-deficient state (< −1.2 eV). In contrast, O-deficient MgO and ▪ have similar (or even stronger) EC decomposition reaction enthalpies of EC than that on the layered-oxide based cathodes (-̃2.0 eV). Our results point out that point defect such as oxygen vacancy O v a c in BMOs, which in most cases are inherently present within the BMOs, induces different reactivity measure on the EC decomposition reaction. Finally, we further point out that the enthalpy of ▪ adsorption on oxygen-deficient surfaces coupled with the O v a c formation energy may serve as practical parameters for designing an effective BMO-based LIB cathode coating material. [Display omitted] • Adsorption and decomposition of ethylene carbonate on metal oxide surfaces. • The decompositions are mostly exothermic relative to the adsorbed state. • The decomposition products are CO 2 , C 2 H 4 , H*, CH 3 CHO*, CH 2 CHO*, and CH 2 CHOCOO*. • The decompositions indirectly contribute to capacity reduction and cell pressure. • Factors affecting the decomposition thermodynamic driving force are discussed. [ABSTRACT FROM AUTHOR]
ISSN:02540584
DOI:10.1016/j.matchemphys.2025.131513