Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules

Livia Giordano; Thomas M. Østergaard; Sokseiha Muy; Yang Yu; Nenian Charles; Soo Kim; Yirui Zhang; Filippo Maglia; Roland Jung; Isaac Lund; Jan Rossmeisl; Yang Shao-horn

doi:10.1021/acs.chemmater.9b00767

Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules

Livia Giordano, Thomas M. Østergaard, Sokseiha Muy, Yang Yu, Nenian Charles, Soo Kim, Yirui Zhang, Filippo Maglia, Roland Jung, Isaac Lund, Jan Rossmeisl, Yang Shao-horn

Department of Chemistry

8 Citations (Scopus)

Abstract

The hydrogen adsorption energetics on the surface of inorganic compounds can be used to predict electrolyte stability in Li-ion batteries and catalytic activity for selective oxidation of small molecules such as H₂ and CH₄. Using first-principles density functional theory (DFT), the hydrogen adsorption was found to be unfavorable on high-band-gap insulators, which could be attributed to a lower energy level associated with adsorbed hydrogen relative to the bottom of the conduction band. In contrast, the hydrogen adsorption was shown to be the most favorable on metallic and semiconducting compounds, which results from an electron transfer from adsorbed hydrogen to the Fermi level or the bottom of the conduction band. Of significance, computed hydrogen adsorption energetics on insulating, semiconducting, and metallic oxides; phosphates; fluorides; and sulfides were decreased by lowering the ligand p band center, while the energy penalty for ligand vacancy formation was increased, indicative of decreased surface reducibility. A statistical regression analysis, where 16 structural and electronic parameters such as metal-ligand distance, electronegativity difference, Bader charges, bulk and surface metal and ligand band centers, band gap, ligand band width, and work function were examined, further showed that the surface ligand p band center is the most accurate single descriptor that governs the hydrogen adsorption tendency, and additional considerations of the band gap and average metal-ligand distance further reconcile the differences among compounds with different ligands/structures, whose ligand bands are different in shape and width. We discuss the implications of these findings for passivating coatings and design of catalysts and the need for novel theoretical methods to accurately estimate these quantities from first principles. These results establish a universal design principle for future high-throughput studies aiming to design electrode surfaces to minimize electrolyte oxidation by dehydrogenation in Li-ion batteries and enhance the H-H and C-H activation for selective oxidation catalysis.

Original language	English
Journal	Chemistry of Materials
Volume	31
Issue number	15
Pages (from-to)	5464-5474
ISSN	0897-4756
DOIs	https://doi.org/10.1021/acs.chemmater.9b00767
Publication status	Published - 13 Aug 2019

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10.1021/acs.chemmater.9b00767

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Giordano, L., Østergaard, T. M., Muy, S., Yu, Y., Charles, N., Kim, S., Zhang, Y., Maglia, F., Jung, R., Lund, I., Rossmeisl, J., & Shao-horn, Y. (2019). Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules. Chemistry of Materials, 31(15), 5464-5474. https://doi.org/10.1021/acs.chemmater.9b00767

Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules. / Giordano, Livia; Østergaard, Thomas M.; Muy, Sokseiha et al.
In: Chemistry of Materials, Vol. 31, No. 15, 13.08.2019, p. 5464-5474.

Research output: Contribution to journal › Journal article › Research › peer-review

Giordano, L, Østergaard, TM, Muy, S, Yu, Y, Charles, N, Kim, S, Zhang, Y, Maglia, F, Jung, R, Lund, I, Rossmeisl, J & Shao-horn, Y 2019, 'Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules', Chemistry of Materials, vol. 31, no. 15, pp. 5464-5474. https://doi.org/10.1021/acs.chemmater.9b00767

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title = "Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules",

abstract = "The hydrogen adsorption energetics on the surface of inorganic compounds can be used to predict electrolyte stability in Li-ion batteries and catalytic activity for selective oxidation of small molecules such as H2 and CH4. Using first-principles density functional theory (DFT), the hydrogen adsorption was found to be unfavorable on high-band-gap insulators, which could be attributed to a lower energy level associated with adsorbed hydrogen relative to the bottom of the conduction band. In contrast, the hydrogen adsorption was shown to be the most favorable on metallic and semiconducting compounds, which results from an electron transfer from adsorbed hydrogen to the Fermi level or the bottom of the conduction band. Of significance, computed hydrogen adsorption energetics on insulating, semiconducting, and metallic oxides; phosphates; fluorides; and sulfides were decreased by lowering the ligand p band center, while the energy penalty for ligand vacancy formation was increased, indicative of decreased surface reducibility. A statistical regression analysis, where 16 structural and electronic parameters such as metal-ligand distance, electronegativity difference, Bader charges, bulk and surface metal and ligand band centers, band gap, ligand band width, and work function were examined, further showed that the surface ligand p band center is the most accurate single descriptor that governs the hydrogen adsorption tendency, and additional considerations of the band gap and average metal-ligand distance further reconcile the differences among compounds with different ligands/structures, whose ligand bands are different in shape and width. We discuss the implications of these findings for passivating coatings and design of catalysts and the need for novel theoretical methods to accurately estimate these quantities from first principles. These results establish a universal design principle for future high-throughput studies aiming to design electrode surfaces to minimize electrolyte oxidation by dehydrogenation in Li-ion batteries and enhance the H-H and C-H activation for selective oxidation catalysis.",

author = "Livia Giordano and {\O}stergaard, {Thomas M.} and Sokseiha Muy and Yang Yu and Nenian Charles and Soo Kim and Yirui Zhang and Filippo Maglia and Roland Jung and Isaac Lund and Jan Rossmeisl and Yang Shao-horn",

year = "2019",

month = aug,

day = "13",

doi = "10.1021/acs.chemmater.9b00767",

language = "English",

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pages = "5464--5474",

journal = "Chemistry of Materials",

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TY - JOUR

T1 - Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules

AU - Giordano, Livia

AU - Østergaard, Thomas M.

AU - Muy, Sokseiha

AU - Yu, Yang

AU - Charles, Nenian

AU - Kim, Soo

AU - Zhang, Yirui

AU - Maglia, Filippo

AU - Jung, Roland

AU - Lund, Isaac

AU - Rossmeisl, Jan

AU - Shao-horn, Yang

PY - 2019/8/13

Y1 - 2019/8/13

N2 - The hydrogen adsorption energetics on the surface of inorganic compounds can be used to predict electrolyte stability in Li-ion batteries and catalytic activity for selective oxidation of small molecules such as H2 and CH4. Using first-principles density functional theory (DFT), the hydrogen adsorption was found to be unfavorable on high-band-gap insulators, which could be attributed to a lower energy level associated with adsorbed hydrogen relative to the bottom of the conduction band. In contrast, the hydrogen adsorption was shown to be the most favorable on metallic and semiconducting compounds, which results from an electron transfer from adsorbed hydrogen to the Fermi level or the bottom of the conduction band. Of significance, computed hydrogen adsorption energetics on insulating, semiconducting, and metallic oxides; phosphates; fluorides; and sulfides were decreased by lowering the ligand p band center, while the energy penalty for ligand vacancy formation was increased, indicative of decreased surface reducibility. A statistical regression analysis, where 16 structural and electronic parameters such as metal-ligand distance, electronegativity difference, Bader charges, bulk and surface metal and ligand band centers, band gap, ligand band width, and work function were examined, further showed that the surface ligand p band center is the most accurate single descriptor that governs the hydrogen adsorption tendency, and additional considerations of the band gap and average metal-ligand distance further reconcile the differences among compounds with different ligands/structures, whose ligand bands are different in shape and width. We discuss the implications of these findings for passivating coatings and design of catalysts and the need for novel theoretical methods to accurately estimate these quantities from first principles. These results establish a universal design principle for future high-throughput studies aiming to design electrode surfaces to minimize electrolyte oxidation by dehydrogenation in Li-ion batteries and enhance the H-H and C-H activation for selective oxidation catalysis.

AB - The hydrogen adsorption energetics on the surface of inorganic compounds can be used to predict electrolyte stability in Li-ion batteries and catalytic activity for selective oxidation of small molecules such as H2 and CH4. Using first-principles density functional theory (DFT), the hydrogen adsorption was found to be unfavorable on high-band-gap insulators, which could be attributed to a lower energy level associated with adsorbed hydrogen relative to the bottom of the conduction band. In contrast, the hydrogen adsorption was shown to be the most favorable on metallic and semiconducting compounds, which results from an electron transfer from adsorbed hydrogen to the Fermi level or the bottom of the conduction band. Of significance, computed hydrogen adsorption energetics on insulating, semiconducting, and metallic oxides; phosphates; fluorides; and sulfides were decreased by lowering the ligand p band center, while the energy penalty for ligand vacancy formation was increased, indicative of decreased surface reducibility. A statistical regression analysis, where 16 structural and electronic parameters such as metal-ligand distance, electronegativity difference, Bader charges, bulk and surface metal and ligand band centers, band gap, ligand band width, and work function were examined, further showed that the surface ligand p band center is the most accurate single descriptor that governs the hydrogen adsorption tendency, and additional considerations of the band gap and average metal-ligand distance further reconcile the differences among compounds with different ligands/structures, whose ligand bands are different in shape and width. We discuss the implications of these findings for passivating coatings and design of catalysts and the need for novel theoretical methods to accurately estimate these quantities from first principles. These results establish a universal design principle for future high-throughput studies aiming to design electrode surfaces to minimize electrolyte oxidation by dehydrogenation in Li-ion batteries and enhance the H-H and C-H activation for selective oxidation catalysis.

U2 - 10.1021/acs.chemmater.9b00767

DO - 10.1021/acs.chemmater.9b00767

M3 - Journal article

SN - 0897-4756

VL - 31

SP - 5464

EP - 5474

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 15

ER -

Ligand-Dependent Energetics for Dehydrogenation: Implications in Li-Ion Battery Electrolyte Stability and Selective Oxidation Catalysis of Hydrogen-Containing Molecules

Abstract

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