Elucidating the Limit of Li Insertion into the Spinel Li4Ti5O12

Haodong Liu; Zhuoying Zhu; Jason Huang; Xin He; Yan Chen; Rui Zhang; Ruoqian Lin; Yejing Li; Sicen Yu; Xing Xing; Qizhang Yan; Xiangguo Li; Matthew J. Frost; Ke An; Jun Feng; Robert Kostecki; Huolin Xin; Shyue Ping Ong; Ping Liu

doi:10.1021/acsmaterialslett.9b00099

Elucidating the Limit of Li Insertion into the Spinel Li₄Ti₅O₁₂

Haodong Liu, Zhuoying Zhu, Jason Huang, Xin He, Yan Chen, Rui Zhang, Ruoqian Lin, Yejing Li, Sicen Yu, Xing Xing, Qizhang Yan, Xiangguo Li, Matthew J. Frost, Ke An, Jun Feng, Robert Kostecki, Huolin Xin, Shyue Ping Ong, Ping Liu

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Abstract

In this work, we show that the well-known lithium-ion anode material, Li₄Ti₅O₁₂, exhibits exceptionally high initial capacity of 310 mAh g^-1 when it is discharged to 0.01 V. It maintains a reversible capacity of 230 mAh g^-1, far exceeding the "theoretical" capacity of 175 mAh g^-1 when this anode is lithiated to the composition Li₇Ti₅O₁₂. Neutron diffraction analyses identify that additional Li reversibly enters into the Li₇Ti₅O₁₂ to form Li₈Ti₅O₁₂. density functional theory (DFT) calculations reveal the average potentials of the Li₄Ti₅O₁₂ to Li₇Ti₅O₁₂ step and the Li₇Ti₅O₁₂ to Li₈Ti₅O₁₂ step are 1.57 and 0.19 V, respectively, which are in excellent agreement with experimental results. Transmission electron microscopy (TEM) studies confirm that the irreversible capacity of Li₄Ti₅O₁₂ during its first cycle originates from the formation of a solid electrolyte interface (SEI) layer. This work clarifies the fundamental lithiation mechanism of the Li₄Ti₅O₁₂, when lithiated to 0.01 V vs Li.

Original language	English
Pages (from-to)	96-102
Number of pages	7
Journal	ACS Materials Letters
Volume	1
Issue number	1
DOIs	https://doi.org/10.1021/acsmaterialslett.9b00099
State	Published - Jul 1 2019

Funding

This work was supported by the Office of Vehicle Technologies of the U.S. Department of Energy, through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium), under Contract No. DE-EE0007764. Part of the work used the UCSD-MTI Battery Fabrication Facility and the UCSD-Arbin Battery Testing Facility. Z.Z., X.L. and S.P.O. acknowledge funding from the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0012118, for the computational part of this work, as well as computing resources provided by Triton Shared Computing Cluster (TSCC) at UC San Diego, the National Energy Research Scientific Computing Center (NERSC), and the Extreme Science and Engineering Discovery Environment (XSEDE) supported by the National Science Foundation, under Grant No. ACI-1053575. Neutron diffraction work was carried out at the Spallation Neutron Source (SNS), which is the U.S. Department of Energy (DOE) user facility at the Oak Ridge National Laboratory, sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences. Work done by R.Z. and H.X. is supported, in part, by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE), under the Award No. DE-EE0008444. R.L. is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program, including the Battery500 Consortium, under Contract No. DE-SC0012704. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory, under Contract No. DE-SC0012704.

Funders	Funder number
Battery500 Consortium	DE-EE0007764
Scientific User Facilities Division
Triton Shared Computing Cluster
National Science Foundation	ACI-1053575
U.S. Department of Energy
Office of Science
Office of Energy Efficiency and Renewable Energy	DE-EE0008444, DE-SC0012704
Basic Energy Sciences	DE-SC0012118
Brookhaven National Laboratory
University of California, San Diego
Vehicle Technologies Office

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title = "Elucidating the Limit of Li Insertion into the Spinel Li4Ti5O12 ",

abstract = "In this work, we show that the well-known lithium-ion anode material, Li4Ti5O12, exhibits exceptionally high initial capacity of 310 mAh g-1 when it is discharged to 0.01 V. It maintains a reversible capacity of 230 mAh g-1, far exceeding the {"}theoretical{"} capacity of 175 mAh g-1 when this anode is lithiated to the composition Li7Ti5O12. Neutron diffraction analyses identify that additional Li reversibly enters into the Li7Ti5O12 to form Li8Ti5O12. density functional theory (DFT) calculations reveal the average potentials of the Li4Ti5O12 to Li7Ti5O12 step and the Li7Ti5O12 to Li8Ti5O12 step are 1.57 and 0.19 V, respectively, which are in excellent agreement with experimental results. Transmission electron microscopy (TEM) studies confirm that the irreversible capacity of Li4Ti5O12 during its first cycle originates from the formation of a solid electrolyte interface (SEI) layer. This work clarifies the fundamental lithiation mechanism of the Li4Ti5O12, when lithiated to 0.01 V vs Li.",

author = "Haodong Liu and Zhuoying Zhu and Jason Huang and Xin He and Yan Chen and Rui Zhang and Ruoqian Lin and Yejing Li and Sicen Yu and Xing Xing and Qizhang Yan and Xiangguo Li and Frost, {Matthew J.} and Ke An and Jun Feng and Robert Kostecki and Huolin Xin and Ong, {Shyue Ping} and Ping Liu",

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year = "2019",

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doi = "10.1021/acsmaterialslett.9b00099",

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T1 - Elucidating the Limit of Li Insertion into the Spinel Li4Ti5O12

AU - Liu, Haodong

AU - Zhu, Zhuoying

AU - Huang, Jason

AU - He, Xin

AU - Chen, Yan

AU - Zhang, Rui

AU - Lin, Ruoqian

AU - Li, Yejing

AU - Yu, Sicen

AU - Xing, Xing

AU - Yan, Qizhang

AU - Li, Xiangguo

AU - Frost, Matthew J.

AU - An, Ke

AU - Feng, Jun

AU - Kostecki, Robert

AU - Xin, Huolin

AU - Ong, Shyue Ping

AU - Liu, Ping

PY - 2019/7/1

Y1 - 2019/7/1

N2 - In this work, we show that the well-known lithium-ion anode material, Li4Ti5O12, exhibits exceptionally high initial capacity of 310 mAh g-1 when it is discharged to 0.01 V. It maintains a reversible capacity of 230 mAh g-1, far exceeding the "theoretical" capacity of 175 mAh g-1 when this anode is lithiated to the composition Li7Ti5O12. Neutron diffraction analyses identify that additional Li reversibly enters into the Li7Ti5O12 to form Li8Ti5O12. density functional theory (DFT) calculations reveal the average potentials of the Li4Ti5O12 to Li7Ti5O12 step and the Li7Ti5O12 to Li8Ti5O12 step are 1.57 and 0.19 V, respectively, which are in excellent agreement with experimental results. Transmission electron microscopy (TEM) studies confirm that the irreversible capacity of Li4Ti5O12 during its first cycle originates from the formation of a solid electrolyte interface (SEI) layer. This work clarifies the fundamental lithiation mechanism of the Li4Ti5O12, when lithiated to 0.01 V vs Li.

AB - In this work, we show that the well-known lithium-ion anode material, Li4Ti5O12, exhibits exceptionally high initial capacity of 310 mAh g-1 when it is discharged to 0.01 V. It maintains a reversible capacity of 230 mAh g-1, far exceeding the "theoretical" capacity of 175 mAh g-1 when this anode is lithiated to the composition Li7Ti5O12. Neutron diffraction analyses identify that additional Li reversibly enters into the Li7Ti5O12 to form Li8Ti5O12. density functional theory (DFT) calculations reveal the average potentials of the Li4Ti5O12 to Li7Ti5O12 step and the Li7Ti5O12 to Li8Ti5O12 step are 1.57 and 0.19 V, respectively, which are in excellent agreement with experimental results. Transmission electron microscopy (TEM) studies confirm that the irreversible capacity of Li4Ti5O12 during its first cycle originates from the formation of a solid electrolyte interface (SEI) layer. This work clarifies the fundamental lithiation mechanism of the Li4Ti5O12, when lithiated to 0.01 V vs Li.

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Elucidating the Limit of Li Insertion into the Spinel Li₄Ti₅O₁₂

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