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Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries

[Image: see text] The incompatibility of lithium intercalation electrodes with water has impeded the development of aqueous Li-ion batteries. The key challenge is protons which are generated by water dissociation and deform the electrode structures through intercalation. Distinct from previous appro...

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Autores principales: Oh, Hyunjeong, Shin, Seung-Jae, Choi, Eunjin, Yamagishi, Hirona, Ohta, Toshiaki, Yabuuchi, Naoaki, Jung, Hun-Gi, Kim, Hyungjun, Byon, Hye Ryung
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10206596/
https://www.ncbi.nlm.nih.gov/pubmed/37234123
http://dx.doi.org/10.1021/jacsau.3c00061
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author Oh, Hyunjeong
Shin, Seung-Jae
Choi, Eunjin
Yamagishi, Hirona
Ohta, Toshiaki
Yabuuchi, Naoaki
Jung, Hun-Gi
Kim, Hyungjun
Byon, Hye Ryung
author_facet Oh, Hyunjeong
Shin, Seung-Jae
Choi, Eunjin
Yamagishi, Hirona
Ohta, Toshiaki
Yabuuchi, Naoaki
Jung, Hun-Gi
Kim, Hyungjun
Byon, Hye Ryung
author_sort Oh, Hyunjeong
collection PubMed
description [Image: see text] The incompatibility of lithium intercalation electrodes with water has impeded the development of aqueous Li-ion batteries. The key challenge is protons which are generated by water dissociation and deform the electrode structures through intercalation. Distinct from previous approaches utilizing large amounts of electrolyte salts or artificial solid-protective films, we developed liquid-phase protective layers on LiCoO(2) (LCO) using a moderate concentration of 0.5∼3 mol kg(–1) lithium sulfate. Sulfate ion strengthened the hydrogen-bond network and easily formed ion pairs with Li(+), showing strong kosmotropic and hard base characteristics. Our quantum mechanics/molecular mechanics (QM/MM) simulations revealed that sulfate ion paired with Li(+) helped stabilize the LCO surface and reduced the density of free water in the interface region below the point of zero charge (PZC) potential. In addition, in situ electrochemical surface-enhanced infrared absorption spectroscopy (SEIRAS) proved the appearance of inner-sphere sulfate complexes above the PZC potential, serving as the protective layers of LCO. The role of anions in stabilizing LCO was correlated with kosmotropic strength (sulfate > nitrate > perchlorate > bistriflimide (TFSI(–))) and explained better galvanostatic cyclability in LCO cells.
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spelling pubmed-102065962023-05-25 Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries Oh, Hyunjeong Shin, Seung-Jae Choi, Eunjin Yamagishi, Hirona Ohta, Toshiaki Yabuuchi, Naoaki Jung, Hun-Gi Kim, Hyungjun Byon, Hye Ryung JACS Au [Image: see text] The incompatibility of lithium intercalation electrodes with water has impeded the development of aqueous Li-ion batteries. The key challenge is protons which are generated by water dissociation and deform the electrode structures through intercalation. Distinct from previous approaches utilizing large amounts of electrolyte salts or artificial solid-protective films, we developed liquid-phase protective layers on LiCoO(2) (LCO) using a moderate concentration of 0.5∼3 mol kg(–1) lithium sulfate. Sulfate ion strengthened the hydrogen-bond network and easily formed ion pairs with Li(+), showing strong kosmotropic and hard base characteristics. Our quantum mechanics/molecular mechanics (QM/MM) simulations revealed that sulfate ion paired with Li(+) helped stabilize the LCO surface and reduced the density of free water in the interface region below the point of zero charge (PZC) potential. In addition, in situ electrochemical surface-enhanced infrared absorption spectroscopy (SEIRAS) proved the appearance of inner-sphere sulfate complexes above the PZC potential, serving as the protective layers of LCO. The role of anions in stabilizing LCO was correlated with kosmotropic strength (sulfate > nitrate > perchlorate > bistriflimide (TFSI(–))) and explained better galvanostatic cyclability in LCO cells. American Chemical Society 2023-04-28 /pmc/articles/PMC10206596/ /pubmed/37234123 http://dx.doi.org/10.1021/jacsau.3c00061 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Oh, Hyunjeong
Shin, Seung-Jae
Choi, Eunjin
Yamagishi, Hirona
Ohta, Toshiaki
Yabuuchi, Naoaki
Jung, Hun-Gi
Kim, Hyungjun
Byon, Hye Ryung
Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries
title Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries
title_full Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries
title_fullStr Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries
title_full_unstemmed Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries
title_short Anion-Induced Interfacial Liquid Layers on LiCoO(2) in Salt-in-Water Lithium-Ion Batteries
title_sort anion-induced interfacial liquid layers on licoo(2) in salt-in-water lithium-ion batteries
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10206596/
https://www.ncbi.nlm.nih.gov/pubmed/37234123
http://dx.doi.org/10.1021/jacsau.3c00061
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