Expanded lithiation of titanium disulfide: Reaction kinetics of multi-step conversion reaction

Maosen Fu; Zhenpeng Yao; Xiao Ma; Hui Dong; Ke Sun; Sooyeon Hwang; Enyuan Hu; Hong Gan; Yan Yao; Eric A. Stach; Chris Wolverton; Dong Su

doi:10.1016/j.nanoen.2019.103882

Expanded lithiation of titanium disulfide: Reaction kinetics of multi-step conversion reaction

Maosen Fu, Zhenpeng Yao, Xiao Ma, Hui Dong, Ke Sun, Sooyeon Hwang, Enyuan Hu, Hong Gan, Yan Yao, Eric A. Stach, Chris Wolverton, Dong Su^*

^*Corresponding author for this work

Materials Science and Engineering

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

21 Scopus citations

Abstract

Phase evolution during a thorough Li ion's insertion of electrode materials governs their battery performance during charge and discharge. Here we investigated the lithiation pathway of titanium disulfide using in situ TEM combined with synchrotron-based pair distribution function measurement and first-principles calculations. A 2D intercalation reaction proceeds along with a transition from van der Waals interaction between Ti–S slabs to the covalent bonding of S–Li–S, with no symmetry broken. Further lithiation triggers unconventionally multiple step conversion reactions as proved: LiTiS₂→TiS→Ti₂S→Ti. The conversion reaction pathway is also verified in fully discharged sample in coin-cell. The expanded conversion chemistry is supposed to increase the capacity of TiS₂ electrode and downgrade the cyclability, whereas the existence of intermediate phases shows the promise of improving the reversibility with a successful control of the state of charge.

Original language	English (US)
Article number	103882
Journal	Nano Energy
Volume	63
DOIs	https://doi.org/10.1016/j.nanoen.2019.103882
State	Published - Sep 2019

Funding

Electron microscopy work was performed at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy , Office of Basic Energy Science , under contract No. DE-SC0012704 . M.Fu acknowledge the support of Visiting Scholar Research Program of NPU , the Fundamental Research Funds for the Central Universities ( 31020195C001 ) and Innovation and Development Program of Shaanxi Province ( 2017KTPT-03 ). Z.Y. (DFT calculations, analysis of results) and C.W. (leadership of DFT calculations) were supported as part of the Center for Electrochemical Energy Science (CEES), an Energy Frontier Research Center funded by the U.S. Department of Energy , Office of Science , Basic Energy Sciences under Award No. DE-AC02-06CH11357 . The authors gratefully acknowledge the computing resources from the National Energy Research Scientific Computing Center , a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 . This research used 28-ID-2 (XPD) of the National Synchrotron Light Source II, a U.S. Department of Energy Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704 . H.D. and Y.Y. acknowledges funding support from the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy ( DE-EE0008234 ), UH Technical Gap Fund , and UH High Priority Area Large Equipment Grant . Electron microscopy work was performed at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Science, under contract No. DE-SC0012704. M.Fu acknowledge the support of Visiting Scholar Research Program of NPU, the Fundamental Research Funds for the Central Universities (31020195C001) and Innovation and Development Program of Shaanxi Province (2017KTPT-03). Z.Y. (DFT calculations, analysis of results) and C.W. (leadership of DFT calculations) were supported as part of the Center for Electrochemical Energy Science (CEES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-AC02-06CH11357. The authors gratefully acknowledge the computing resources from the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This research used 28-ID-2 (XPD) of the National Synchrotron Light Source II, a U.S. Department of Energy Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. H.D. and Y.Y. acknowledges funding support from the U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy (DE-EE0008234), UH Technical Gap Fund, and UH High Priority Area Large Equipment Grant.

Keywords

2D metal chalcogenides
Conversion reaction
In situ transmission electron microscopy
Lithiation
Lithium ion battery

ASJC Scopus subject areas

Renewable Energy, Sustainability and the Environment
General Materials Science
Electrical and Electronic Engineering

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.nanoen.2019.103882

Cite this

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title = "Expanded lithiation of titanium disulfide: Reaction kinetics of multi-step conversion reaction",

abstract = "Phase evolution during a thorough Li ion's insertion of electrode materials governs their battery performance during charge and discharge. Here we investigated the lithiation pathway of titanium disulfide using in situ TEM combined with synchrotron-based pair distribution function measurement and first-principles calculations. A 2D intercalation reaction proceeds along with a transition from van der Waals interaction between Ti–S slabs to the covalent bonding of S–Li–S, with no symmetry broken. Further lithiation triggers unconventionally multiple step conversion reactions as proved: LiTiS2→TiS→Ti2S→Ti. The conversion reaction pathway is also verified in fully discharged sample in coin-cell. The expanded conversion chemistry is supposed to increase the capacity of TiS2 electrode and downgrade the cyclability, whereas the existence of intermediate phases shows the promise of improving the reversibility with a successful control of the state of charge.",

keywords = "2D metal chalcogenides, Conversion reaction, In situ transmission electron microscopy, Lithiation, Lithium ion battery",

author = "Maosen Fu and Zhenpeng Yao and Xiao Ma and Hui Dong and Ke Sun and Sooyeon Hwang and Enyuan Hu and Hong Gan and Yan Yao and Stach, {Eric A.} and Chris Wolverton and Dong Su",

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year = "2019",

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doi = "10.1016/j.nanoen.2019.103882",

language = "English (US)",

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T2 - Reaction kinetics of multi-step conversion reaction

AU - Fu, Maosen

AU - Yao, Zhenpeng

AU - Ma, Xiao

AU - Dong, Hui

AU - Sun, Ke

AU - Hwang, Sooyeon

AU - Hu, Enyuan

AU - Gan, Hong

AU - Yao, Yan

AU - Stach, Eric A.

AU - Wolverton, Chris

AU - Su, Dong

PY - 2019/9

Y1 - 2019/9

N2 - Phase evolution during a thorough Li ion's insertion of electrode materials governs their battery performance during charge and discharge. Here we investigated the lithiation pathway of titanium disulfide using in situ TEM combined with synchrotron-based pair distribution function measurement and first-principles calculations. A 2D intercalation reaction proceeds along with a transition from van der Waals interaction between Ti–S slabs to the covalent bonding of S–Li–S, with no symmetry broken. Further lithiation triggers unconventionally multiple step conversion reactions as proved: LiTiS2→TiS→Ti2S→Ti. The conversion reaction pathway is also verified in fully discharged sample in coin-cell. The expanded conversion chemistry is supposed to increase the capacity of TiS2 electrode and downgrade the cyclability, whereas the existence of intermediate phases shows the promise of improving the reversibility with a successful control of the state of charge.

AB - Phase evolution during a thorough Li ion's insertion of electrode materials governs their battery performance during charge and discharge. Here we investigated the lithiation pathway of titanium disulfide using in situ TEM combined with synchrotron-based pair distribution function measurement and first-principles calculations. A 2D intercalation reaction proceeds along with a transition from van der Waals interaction between Ti–S slabs to the covalent bonding of S–Li–S, with no symmetry broken. Further lithiation triggers unconventionally multiple step conversion reactions as proved: LiTiS2→TiS→Ti2S→Ti. The conversion reaction pathway is also verified in fully discharged sample in coin-cell. The expanded conversion chemistry is supposed to increase the capacity of TiS2 electrode and downgrade the cyclability, whereas the existence of intermediate phases shows the promise of improving the reversibility with a successful control of the state of charge.

KW - 2D metal chalcogenides

KW - Conversion reaction

KW - In situ transmission electron microscopy

KW - Lithiation

KW - Lithium ion battery

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Expanded lithiation of titanium disulfide: Reaction kinetics of multi-step conversion reaction

Abstract

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

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