Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na–O2 Batteries

Laura Garcia-Quintana; Nagore Ortiz-Vitoriano; Haijin Zhu; Gene M. Nolis; Javier Herrero-Martín; María Echeverría; Juan Miguel López del Amo; Maria Forsyth; Alan M. Bond; Patrick C. Howlett; Cristina Pozo-Gonzalo

doi:10.1021/acsami.1c20257

Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na–O₂ Batteries

Laura Garcia-Quintana, Nagore Ortiz-Vitoriano^*, Haijin Zhu, Gene M. Nolis, Javier Herrero-Martín, María Echeverría, Juan Miguel López del Amo, Maria Forsyth, Alan M. Bond, Patrick C. Howlett, Cristina Pozo-Gonzalo^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

A series of hybrid electrolytes composed of diglyme and ionic liquids (ILs) have been investigated for Na–O₂ batteries, as a strategy to control the growth and purity of the discharge products during battery operation. The dependence of chemical composition of the ILs on the size, purity, and distribution of the discharge products has been evaluated using a wide range of experimental and spectroscopic techniques. The morphology and composition of the discharge products found in the Na–O₂ cells have a complex dependence on the physicochemical properties of the electrolyte as well as the speciation of the Na⁺ and superoxide radical anion. All of these factors control the nucleation and growth phenomena as well as electrolyte stability. Smaller discharge particle sizes and largely homogeneous (2.7 ± 0.5 μm) sodium superoxide (NaO₂) crystals with only 9% of side products were found in the hybrid electrolyte containing the pyrrolidinium IL with a linear alkyl chain. The long-term cyclability of Na–O₂ batteries with high Coulombic efficiency (>90%) was obtained for this electrolyte with fewer side products (20 cycles at 0.5 mA h cm^–2). In contrast, rapid failure was observed with the use of the phosphonium-based electrolyte, which strongly stabilizes the superoxide anion. A high discharge capacity (4.46 mA h cm^–2) was obtained for the hybrid electrolyte containing the pyrrolidinium-based IL bearing a linear alkyl chain with a slightly lower value (3.11 mA h cm^–2) being obtained when the hybrid electrolyte contained similar pyrrolidinium-based IL bearing an alkoxy chain.

Original language	English
Pages (from-to)	4022-4034
Number of pages	13
Journal	ACS applied materials & interfaces
Volume	14
Issue number	3
DOIs	https://doi.org/10.1021/acsami.1c20257
State	Published - 26 Jan 2022
Externally published	Yes

Keywords

Na solvation
NaO growth mechanism
Na−O battery
diglyme/ionic liquid hybrid electrolyte
superoxide

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10.1021/acsami.1c20257

Cite this

Garcia-Quintana, L., Ortiz-Vitoriano, N., Zhu, H., Nolis, G. M., Herrero-Martín, J., Echeverría, M., López del Amo, J. M., Forsyth, M., Bond, A. M., Howlett, P. C., & Pozo-Gonzalo, C. (2022). Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na–O₂ Batteries. ACS applied materials & interfaces, 14(3), 4022-4034. https://doi.org/10.1021/acsami.1c20257

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title = "Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na–O2 Batteries",

abstract = "A series of hybrid electrolytes composed of diglyme and ionic liquids (ILs) have been investigated for Na–O2 batteries, as a strategy to control the growth and purity of the discharge products during battery operation. The dependence of chemical composition of the ILs on the size, purity, and distribution of the discharge products has been evaluated using a wide range of experimental and spectroscopic techniques. The morphology and composition of the discharge products found in the Na–O2 cells have a complex dependence on the physicochemical properties of the electrolyte as well as the speciation of the Na+ and superoxide radical anion. All of these factors control the nucleation and growth phenomena as well as electrolyte stability. Smaller discharge particle sizes and largely homogeneous (2.7 ± 0.5 μm) sodium superoxide (NaO2) crystals with only 9% of side products were found in the hybrid electrolyte containing the pyrrolidinium IL with a linear alkyl chain. The long-term cyclability of Na–O2 batteries with high Coulombic efficiency (>90%) was obtained for this electrolyte with fewer side products (20 cycles at 0.5 mA h cm–2). In contrast, rapid failure was observed with the use of the phosphonium-based electrolyte, which strongly stabilizes the superoxide anion. A high discharge capacity (4.46 mA h cm–2) was obtained for the hybrid electrolyte containing the pyrrolidinium-based IL bearing a linear alkyl chain with a slightly lower value (3.11 mA h cm–2) being obtained when the hybrid electrolyte contained similar pyrrolidinium-based IL bearing an alkoxy chain.",

keywords = "Na solvation, NaO growth mechanism, Na−O battery, diglyme/ionic liquid hybrid electrolyte, superoxide",

author = "Laura Garcia-Quintana and Nagore Ortiz-Vitoriano and Haijin Zhu and Nolis, {Gene M.} and Javier Herrero-Mart{\'i}n and Mar{\'i}a Echeverr{\'i}a and {L{\'o}pez del Amo}, {Juan Miguel} and Maria Forsyth and Bond, {Alan M.} and Howlett, {Patrick C.} and Cristina Pozo-Gonzalo",

note = "Publisher Copyright: {\textcopyright} 2022 American Chemical Society",

year = "2022",

month = jan,

day = "26",

doi = "10.1021/acsami.1c20257",

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Garcia-Quintana, L, Ortiz-Vitoriano, N, Zhu, H, Nolis, GM, Herrero-Martín, J, Echeverría, M, López del Amo, JM, Forsyth, M, Bond, AM, Howlett, PC & Pozo-Gonzalo, C 2022, 'Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na–O₂ Batteries', ACS applied materials & interfaces, vol. 14, no. 3, pp. 4022-4034. https://doi.org/10.1021/acsami.1c20257

TY - JOUR

T1 - Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na–O2 Batteries

AU - Garcia-Quintana, Laura

AU - Ortiz-Vitoriano, Nagore

AU - Zhu, Haijin

AU - Nolis, Gene M.

AU - Herrero-Martín, Javier

AU - Echeverría, María

AU - López del Amo, Juan Miguel

AU - Forsyth, Maria

AU - Bond, Alan M.

AU - Howlett, Patrick C.

AU - Pozo-Gonzalo, Cristina

PY - 2022/1/26

Y1 - 2022/1/26

N2 - A series of hybrid electrolytes composed of diglyme and ionic liquids (ILs) have been investigated for Na–O2 batteries, as a strategy to control the growth and purity of the discharge products during battery operation. The dependence of chemical composition of the ILs on the size, purity, and distribution of the discharge products has been evaluated using a wide range of experimental and spectroscopic techniques. The morphology and composition of the discharge products found in the Na–O2 cells have a complex dependence on the physicochemical properties of the electrolyte as well as the speciation of the Na+ and superoxide radical anion. All of these factors control the nucleation and growth phenomena as well as electrolyte stability. Smaller discharge particle sizes and largely homogeneous (2.7 ± 0.5 μm) sodium superoxide (NaO2) crystals with only 9% of side products were found in the hybrid electrolyte containing the pyrrolidinium IL with a linear alkyl chain. The long-term cyclability of Na–O2 batteries with high Coulombic efficiency (>90%) was obtained for this electrolyte with fewer side products (20 cycles at 0.5 mA h cm–2). In contrast, rapid failure was observed with the use of the phosphonium-based electrolyte, which strongly stabilizes the superoxide anion. A high discharge capacity (4.46 mA h cm–2) was obtained for the hybrid electrolyte containing the pyrrolidinium-based IL bearing a linear alkyl chain with a slightly lower value (3.11 mA h cm–2) being obtained when the hybrid electrolyte contained similar pyrrolidinium-based IL bearing an alkoxy chain.

AB - A series of hybrid electrolytes composed of diglyme and ionic liquids (ILs) have been investigated for Na–O2 batteries, as a strategy to control the growth and purity of the discharge products during battery operation. The dependence of chemical composition of the ILs on the size, purity, and distribution of the discharge products has been evaluated using a wide range of experimental and spectroscopic techniques. The morphology and composition of the discharge products found in the Na–O2 cells have a complex dependence on the physicochemical properties of the electrolyte as well as the speciation of the Na+ and superoxide radical anion. All of these factors control the nucleation and growth phenomena as well as electrolyte stability. Smaller discharge particle sizes and largely homogeneous (2.7 ± 0.5 μm) sodium superoxide (NaO2) crystals with only 9% of side products were found in the hybrid electrolyte containing the pyrrolidinium IL with a linear alkyl chain. The long-term cyclability of Na–O2 batteries with high Coulombic efficiency (>90%) was obtained for this electrolyte with fewer side products (20 cycles at 0.5 mA h cm–2). In contrast, rapid failure was observed with the use of the phosphonium-based electrolyte, which strongly stabilizes the superoxide anion. A high discharge capacity (4.46 mA h cm–2) was obtained for the hybrid electrolyte containing the pyrrolidinium-based IL bearing a linear alkyl chain with a slightly lower value (3.11 mA h cm–2) being obtained when the hybrid electrolyte contained similar pyrrolidinium-based IL bearing an alkoxy chain.

KW - Na solvation

KW - NaO growth mechanism

KW - Na−O battery

KW - diglyme/ionic liquid hybrid electrolyte

KW - superoxide

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U2 - 10.1021/acsami.1c20257

DO - 10.1021/acsami.1c20257

M3 - 文章

C2 - 35019264

AN - SCOPUS:85123357149

SN - 1944-8244

VL - 14

SP - 4022

EP - 4034

JO - ACS applied materials & interfaces

JF - ACS applied materials & interfaces

IS - 3

ER -

Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na–O₂ Batteries

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Keywords

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