Combined DFT and DEMS investigation of the effect of dopants in secondary zinc‐air batteries

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Abstract

Zinc–air batteries offer the potential of low‐cost energy storage with high specific energy, but at present secondary Zn–air batteries suffer from poor cyclability. To develop economically viable secondary Zn–air batteries, several properties need to be improved: choking of the cathode, catalyzing the oxygen evolution and reduction reactions, limiting dendrite formation and suppressing the hydrogen evolution reaction (HER). Understanding and alleviating HER at the negative electrode in a secondary Zn–air battery is a substantial challenge, for which it is necessary to combine computational and experimental research. Here, we combine differential electrochemical mass spectrometry (DEMS) and density functional theory (DFT) calculations to investigate the fundamental role and stability when cycling in the presence of selected beneficial additives, that is, In and Bi, and Ag as a potentially unfavorable additive. We show that both In and Bi have the desired property for a secondary battery, that is, upon recharging they will remain on the surface, thereby retaining the beneficial effects on Zn dissolution and suppression of HER. This is confirmed by DEMS, where it is observed that In reduces HER and Bi affects the discharge potential beneficially compared to a battery without additives. Using a simple procedure based on adsorption energies calculated with DFT, it is found that Ag suppresses OH adsorption, but, unlike In and Bi, it does not hinder HER. Finally, it is shown that mixing In and Bi is beneficial compared to the additives by themselves as it improves the electrochemical performance and cyclic stability of the secondary Zn–air battery.
Original languageEnglish
JournalChemSusChem (Print)
Volume11
Issue number12
Pages (from-to)1933-1941
ISSN1864-5631
DOIs
Publication statusPublished - 2018

Cite this

@article{e84d03eb326c42319b71fb48a0907cd9,
title = "Combined DFT and DEMS investigation of the effect of dopants in secondary zinc‐air batteries",
abstract = "Zinc–air batteries offer the potential of low‐cost energy storage with high specific energy, but at present secondary Zn–air batteries suffer from poor cyclability. To develop economically viable secondary Zn–air batteries, several properties need to be improved: choking of the cathode, catalyzing the oxygen evolution and reduction reactions, limiting dendrite formation and suppressing the hydrogen evolution reaction (HER). Understanding and alleviating HER at the negative electrode in a secondary Zn–air battery is a substantial challenge, for which it is necessary to combine computational and experimental research. Here, we combine differential electrochemical mass spectrometry (DEMS) and density functional theory (DFT) calculations to investigate the fundamental role and stability when cycling in the presence of selected beneficial additives, that is, In and Bi, and Ag as a potentially unfavorable additive. We show that both In and Bi have the desired property for a secondary battery, that is, upon recharging they will remain on the surface, thereby retaining the beneficial effects on Zn dissolution and suppression of HER. This is confirmed by DEMS, where it is observed that In reduces HER and Bi affects the discharge potential beneficially compared to a battery without additives. Using a simple procedure based on adsorption energies calculated with DFT, it is found that Ag suppresses OH adsorption, but, unlike In and Bi, it does not hinder HER. Finally, it is shown that mixing In and Bi is beneficial compared to the additives by themselves as it improves the electrochemical performance and cyclic stability of the secondary Zn–air battery.",
author = "Steen Lysgaard and Christensen, {Mathias K.} and Hansen, {Heine A.} and {Garc{\'i}a Lastra}, {Juan Maria} and Poul Norby and Tejs Vegge",
year = "2018",
doi = "10.1002/cssc.201800225",
language = "English",
volume = "11",
pages = "1933--1941",
journal = "ChemSusChem (Print)",
issn = "1864-5631",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
number = "12",

}

TY - JOUR

T1 - Combined DFT and DEMS investigation of the effect of dopants in secondary zinc‐air batteries

AU - Lysgaard, Steen

AU - Christensen, Mathias K.

AU - Hansen, Heine A.

AU - García Lastra, Juan Maria

AU - Norby, Poul

AU - Vegge, Tejs

PY - 2018

Y1 - 2018

N2 - Zinc–air batteries offer the potential of low‐cost energy storage with high specific energy, but at present secondary Zn–air batteries suffer from poor cyclability. To develop economically viable secondary Zn–air batteries, several properties need to be improved: choking of the cathode, catalyzing the oxygen evolution and reduction reactions, limiting dendrite formation and suppressing the hydrogen evolution reaction (HER). Understanding and alleviating HER at the negative electrode in a secondary Zn–air battery is a substantial challenge, for which it is necessary to combine computational and experimental research. Here, we combine differential electrochemical mass spectrometry (DEMS) and density functional theory (DFT) calculations to investigate the fundamental role and stability when cycling in the presence of selected beneficial additives, that is, In and Bi, and Ag as a potentially unfavorable additive. We show that both In and Bi have the desired property for a secondary battery, that is, upon recharging they will remain on the surface, thereby retaining the beneficial effects on Zn dissolution and suppression of HER. This is confirmed by DEMS, where it is observed that In reduces HER and Bi affects the discharge potential beneficially compared to a battery without additives. Using a simple procedure based on adsorption energies calculated with DFT, it is found that Ag suppresses OH adsorption, but, unlike In and Bi, it does not hinder HER. Finally, it is shown that mixing In and Bi is beneficial compared to the additives by themselves as it improves the electrochemical performance and cyclic stability of the secondary Zn–air battery.

AB - Zinc–air batteries offer the potential of low‐cost energy storage with high specific energy, but at present secondary Zn–air batteries suffer from poor cyclability. To develop economically viable secondary Zn–air batteries, several properties need to be improved: choking of the cathode, catalyzing the oxygen evolution and reduction reactions, limiting dendrite formation and suppressing the hydrogen evolution reaction (HER). Understanding and alleviating HER at the negative electrode in a secondary Zn–air battery is a substantial challenge, for which it is necessary to combine computational and experimental research. Here, we combine differential electrochemical mass spectrometry (DEMS) and density functional theory (DFT) calculations to investigate the fundamental role and stability when cycling in the presence of selected beneficial additives, that is, In and Bi, and Ag as a potentially unfavorable additive. We show that both In and Bi have the desired property for a secondary battery, that is, upon recharging they will remain on the surface, thereby retaining the beneficial effects on Zn dissolution and suppression of HER. This is confirmed by DEMS, where it is observed that In reduces HER and Bi affects the discharge potential beneficially compared to a battery without additives. Using a simple procedure based on adsorption energies calculated with DFT, it is found that Ag suppresses OH adsorption, but, unlike In and Bi, it does not hinder HER. Finally, it is shown that mixing In and Bi is beneficial compared to the additives by themselves as it improves the electrochemical performance and cyclic stability of the secondary Zn–air battery.

U2 - 10.1002/cssc.201800225

DO - 10.1002/cssc.201800225

M3 - Journal article

VL - 11

SP - 1933

EP - 1941

JO - ChemSusChem (Print)

JF - ChemSusChem (Print)

SN - 1864-5631

IS - 12

ER -