Anion π-πStacking for Improved Lithium Transport in Polymer Electrolytes

Lixin Qiao; Sergio Rodriguez Peña; María Martínez-Ibañez; Alexander Santiago; Itziar Aldalur; Elias Lobato; Eduardo Sanchez-Diez; Yan Zhang; Hegoi Manzano; Haijin Zhu; Maria Forsyth; Michel Armand; Javier Carrasco; Heng Zhang

doi:10.1021/jacs.2c02260

Anion π-πStacking for Improved Lithium Transport in Polymer Electrolytes

Lixin Qiao, Sergio Rodriguez Peña, María Martínez-Ibañez, Alexander Santiago, Itziar Aldalur, Elias Lobato, Eduardo Sanchez-Diez, Yan Zhang, Hegoi Manzano, Haijin Zhu, Maria Forsyth, Michel Armand^*, Javier Carrasco^*, Heng Zhang^*

^*Corresponding author for this work

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

28 Scopus citations

Abstract

Polymer electrolytes (PEs) with excellent flexibility, processability, and good contact with lithium metal (Li°) anodes have attracted substantial attention in both academic and industrial settings. However, conventional poly(ethylene oxide) (PEO)-based PEs suffer from a low lithium-ion transference number (T_Li⁺), leading to a notorious concentration gradient and internal cell polarization. Here, we report two kinds of highly lithium-ion conductive and solvent-free PEs using the benzene-based lithium salts, lithium (benzenesulfonyl)(trifluoromethanesulfonyl)imide (LiBTFSI) and lithium (2,4,6-triisopropylbenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiTPBTFSI), which show significantly improved T_Li⁺and selective lithium-ion conductivity. Using molecular dynamics simulations, we pinpoint the strong π-πstacking interaction between pairs of benzene-based anions as the cause of this improvement. In addition, we show that Li°∥Li° and Li°∥LiFePO₄cells with the LiBTFSI/PEO electrolytes present enhanced cycling performance. By considering π-πstacking interactions as a new molecular-level design route of salts for electrolyte, this work provides an efficient and facile novel strategy for attaining highly selective lithium-ion conductive PEs.

Original language	English
Pages (from-to)	9806-9816
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	144
Issue number	22
DOIs	https://doi.org/10.1021/jacs.2c02260
State	Published - 8 Jun 2022
Externally published	Yes

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Qiao, L., Rodriguez Peña, S., Martínez-Ibañez, M., Santiago, A., Aldalur, I., Lobato, E., Sanchez-Diez, E., Zhang, Y., Manzano, H., Zhu, H., Forsyth, M., Armand, M., Carrasco, J., & Zhang, H. (2022). Anion π-πStacking for Improved Lithium Transport in Polymer Electrolytes. Journal of the American Chemical Society, 144(22), 9806-9816. https://doi.org/10.1021/jacs.2c02260

@article{7e8269b62fe6457abfdad1a0a69f4090,

title = "Anion π-πStacking for Improved Lithium Transport in Polymer Electrolytes",

abstract = "Polymer electrolytes (PEs) with excellent flexibility, processability, and good contact with lithium metal (Li°) anodes have attracted substantial attention in both academic and industrial settings. However, conventional poly(ethylene oxide) (PEO)-based PEs suffer from a low lithium-ion transference number (TLi+), leading to a notorious concentration gradient and internal cell polarization. Here, we report two kinds of highly lithium-ion conductive and solvent-free PEs using the benzene-based lithium salts, lithium (benzenesulfonyl)(trifluoromethanesulfonyl)imide (LiBTFSI) and lithium (2,4,6-triisopropylbenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiTPBTFSI), which show significantly improved TLi+and selective lithium-ion conductivity. Using molecular dynamics simulations, we pinpoint the strong π-πstacking interaction between pairs of benzene-based anions as the cause of this improvement. In addition, we show that Li°∥Li° and Li°∥LiFePO4cells with the LiBTFSI/PEO electrolytes present enhanced cycling performance. By considering π-πstacking interactions as a new molecular-level design route of salts for electrolyte, this work provides an efficient and facile novel strategy for attaining highly selective lithium-ion conductive PEs.",

author = "Lixin Qiao and {Rodriguez Pe{\~n}a}, Sergio and Mar{\'i}a Mart{\'i}nez-Iba{\~n}ez and Alexander Santiago and Itziar Aldalur and Elias Lobato and Eduardo Sanchez-Diez and Yan Zhang and Hegoi Manzano and Haijin Zhu and Maria Forsyth and Michel Armand and Javier Carrasco and Heng Zhang",

year = "2022",

month = jun,

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doi = "10.1021/jacs.2c02260",

language = "英语",

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Qiao, L, Rodriguez Peña, S, Martínez-Ibañez, M, Santiago, A, Aldalur, I, Lobato, E, Sanchez-Diez, E, Zhang, Y, Manzano, H, Zhu, H, Forsyth, M, Armand, M, Carrasco, J & Zhang, H 2022, 'Anion π-πStacking for Improved Lithium Transport in Polymer Electrolytes', Journal of the American Chemical Society, vol. 144, no. 22, pp. 9806-9816. https://doi.org/10.1021/jacs.2c02260

TY - JOUR

T1 - Anion π-πStacking for Improved Lithium Transport in Polymer Electrolytes

AU - Qiao, Lixin

AU - Rodriguez Peña, Sergio

AU - Martínez-Ibañez, María

AU - Santiago, Alexander

AU - Aldalur, Itziar

AU - Lobato, Elias

AU - Sanchez-Diez, Eduardo

AU - Zhang, Yan

AU - Manzano, Hegoi

AU - Zhu, Haijin

AU - Forsyth, Maria

AU - Armand, Michel

AU - Carrasco, Javier

AU - Zhang, Heng

PY - 2022/6/8

Y1 - 2022/6/8

N2 - Polymer electrolytes (PEs) with excellent flexibility, processability, and good contact with lithium metal (Li°) anodes have attracted substantial attention in both academic and industrial settings. However, conventional poly(ethylene oxide) (PEO)-based PEs suffer from a low lithium-ion transference number (TLi+), leading to a notorious concentration gradient and internal cell polarization. Here, we report two kinds of highly lithium-ion conductive and solvent-free PEs using the benzene-based lithium salts, lithium (benzenesulfonyl)(trifluoromethanesulfonyl)imide (LiBTFSI) and lithium (2,4,6-triisopropylbenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiTPBTFSI), which show significantly improved TLi+and selective lithium-ion conductivity. Using molecular dynamics simulations, we pinpoint the strong π-πstacking interaction between pairs of benzene-based anions as the cause of this improvement. In addition, we show that Li°∥Li° and Li°∥LiFePO4cells with the LiBTFSI/PEO electrolytes present enhanced cycling performance. By considering π-πstacking interactions as a new molecular-level design route of salts for electrolyte, this work provides an efficient and facile novel strategy for attaining highly selective lithium-ion conductive PEs.

AB - Polymer electrolytes (PEs) with excellent flexibility, processability, and good contact with lithium metal (Li°) anodes have attracted substantial attention in both academic and industrial settings. However, conventional poly(ethylene oxide) (PEO)-based PEs suffer from a low lithium-ion transference number (TLi+), leading to a notorious concentration gradient and internal cell polarization. Here, we report two kinds of highly lithium-ion conductive and solvent-free PEs using the benzene-based lithium salts, lithium (benzenesulfonyl)(trifluoromethanesulfonyl)imide (LiBTFSI) and lithium (2,4,6-triisopropylbenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiTPBTFSI), which show significantly improved TLi+and selective lithium-ion conductivity. Using molecular dynamics simulations, we pinpoint the strong π-πstacking interaction between pairs of benzene-based anions as the cause of this improvement. In addition, we show that Li°∥Li° and Li°∥LiFePO4cells with the LiBTFSI/PEO electrolytes present enhanced cycling performance. By considering π-πstacking interactions as a new molecular-level design route of salts for electrolyte, this work provides an efficient and facile novel strategy for attaining highly selective lithium-ion conductive PEs.

UR - http://www.scopus.com/inward/record.url?scp=85131771941&partnerID=8YFLogxK

U2 - 10.1021/jacs.2c02260

DO - 10.1021/jacs.2c02260

M3 - 文章

C2 - 35638261

AN - SCOPUS:85131771941

SN - 0002-7863

VL - 144

SP - 9806

EP - 9816

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 22

ER -

Anion π-πStacking for Improved Lithium Transport in Polymer Electrolytes

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