Fluorination-guided Li-anchoring behaviors on phthalocyanines

Understanding the interactions between metallic lithium (Li) and the anchoring sites/groups is essential for the design of stable host materials and artificial interphases in lithium metal batteries (LMBs). Here, we investigate the interactions of lithium with the polar organic functional groups in...

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Main Authors: Lian, Xu, Ma, Zhirui, Zhang, Zhonghan, Yang, Jinlin, Liu, Yuan, Gu, Chengding, Sun, Shuo, Ding, Honghe, Hu, Jun, Zhu, Junfa, Li, Shuzhou, Chen, Wei
Other Authors: School of Materials Science and Engineering
Format: Article
Language:English
Published: 2022
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Online Access:https://hdl.handle.net/10356/160167
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-1601672022-07-14T02:25:14Z Fluorination-guided Li-anchoring behaviors on phthalocyanines Lian, Xu Ma, Zhirui Zhang, Zhonghan Yang, Jinlin Liu, Yuan Gu, Chengding Sun, Shuo Ding, Honghe Hu, Jun Zhu, Junfa Li, Shuzhou Chen, Wei School of Materials Science and Engineering Engineering::Materials Lithium Metal Anodes Copper-Phthalocyanine Understanding the interactions between metallic lithium (Li) and the anchoring sites/groups is essential for the design of stable host materials and artificial interphases in lithium metal batteries (LMBs). Here, we investigate the interactions of lithium with the polar organic functional groups in copper(II) hexadecafluorophthalocyanine (F16CuPc) and copper(II) phthalocyanine (CuPc) through the combination of in-situ X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), synchrotron-based near-edge X-ray absorption fine structures (NEXAFS), and density functional theory (DFT) calculations. It is revealed that the highly polar C-F bonds can anchor the Li atom via ionic Li-F interaction around the outer aza bridge N atoms in F16CuPc, while Li tends to interact with the inner pyrrolic N atoms around the central Cu in CuPc. The central Cu(II) ions in both molecules are reduced to Cu(I) upon interaction with Li. Electrons are transferred from Li to the lowest unoccupied molecular orbitals (LUMO) of both F16CuPc and CuPc molecules, as revealed by the UPS and NEXAFS measurements. Our systematic study can shed light on the design of anode materials by adding polar functional groups for applications in lithium metal batteries (LMBs). Ministry of Education (MOE) The authors acknowledge the financial support from the Natural Science Foundation of China (U2032147), Singapore MOE Tier II grant R143-000-A29-112, and Academic Research Fund Tie I grant RG104/18. 2022-07-14T02:25:14Z 2022-07-14T02:25:14Z 2021 Journal Article Lian, X., Ma, Z., Zhang, Z., Yang, J., Liu, Y., Gu, C., Sun, S., Ding, H., Hu, J., Zhu, J., Li, S. & Chen, W. (2021). Fluorination-guided Li-anchoring behaviors on phthalocyanines. Journal of Physical Chemistry C, 125(15), 8236-8243. https://dx.doi.org/10.1021/acs.jpcc.1c00831 1932-7447 https://hdl.handle.net/10356/160167 10.1021/acs.jpcc.1c00831 2-s2.0-85105050472 15 125 8236 8243 en R143-000-A29-112 RG104/18 Journal of Physical Chemistry C © 2021 American Chemical Society. All rights reserved.
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering::Materials
Lithium Metal Anodes
Copper-Phthalocyanine
spellingShingle Engineering::Materials
Lithium Metal Anodes
Copper-Phthalocyanine
Lian, Xu
Ma, Zhirui
Zhang, Zhonghan
Yang, Jinlin
Liu, Yuan
Gu, Chengding
Sun, Shuo
Ding, Honghe
Hu, Jun
Zhu, Junfa
Li, Shuzhou
Chen, Wei
Fluorination-guided Li-anchoring behaviors on phthalocyanines
description Understanding the interactions between metallic lithium (Li) and the anchoring sites/groups is essential for the design of stable host materials and artificial interphases in lithium metal batteries (LMBs). Here, we investigate the interactions of lithium with the polar organic functional groups in copper(II) hexadecafluorophthalocyanine (F16CuPc) and copper(II) phthalocyanine (CuPc) through the combination of in-situ X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), synchrotron-based near-edge X-ray absorption fine structures (NEXAFS), and density functional theory (DFT) calculations. It is revealed that the highly polar C-F bonds can anchor the Li atom via ionic Li-F interaction around the outer aza bridge N atoms in F16CuPc, while Li tends to interact with the inner pyrrolic N atoms around the central Cu in CuPc. The central Cu(II) ions in both molecules are reduced to Cu(I) upon interaction with Li. Electrons are transferred from Li to the lowest unoccupied molecular orbitals (LUMO) of both F16CuPc and CuPc molecules, as revealed by the UPS and NEXAFS measurements. Our systematic study can shed light on the design of anode materials by adding polar functional groups for applications in lithium metal batteries (LMBs).
author2 School of Materials Science and Engineering
author_facet School of Materials Science and Engineering
Lian, Xu
Ma, Zhirui
Zhang, Zhonghan
Yang, Jinlin
Liu, Yuan
Gu, Chengding
Sun, Shuo
Ding, Honghe
Hu, Jun
Zhu, Junfa
Li, Shuzhou
Chen, Wei
format Article
author Lian, Xu
Ma, Zhirui
Zhang, Zhonghan
Yang, Jinlin
Liu, Yuan
Gu, Chengding
Sun, Shuo
Ding, Honghe
Hu, Jun
Zhu, Junfa
Li, Shuzhou
Chen, Wei
author_sort Lian, Xu
title Fluorination-guided Li-anchoring behaviors on phthalocyanines
title_short Fluorination-guided Li-anchoring behaviors on phthalocyanines
title_full Fluorination-guided Li-anchoring behaviors on phthalocyanines
title_fullStr Fluorination-guided Li-anchoring behaviors on phthalocyanines
title_full_unstemmed Fluorination-guided Li-anchoring behaviors on phthalocyanines
title_sort fluorination-guided li-anchoring behaviors on phthalocyanines
publishDate 2022
url https://hdl.handle.net/10356/160167
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