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Nano Research 2019, 12(7): 1675-1681 https://doi.org/10.1007/s12274-019-2421-9
Research Article | Issue | Published: 08 May 2019

Atomic-scale structural and chemical evolution of Li3V2(PO4)3 cathode cycled at high voltage window

Show Author's Information Shulin Chen1,2,3,  Jian Zou1,  Yuehui Li3,  Ning Li3,  Mei Wu3,  Jinghuang Lin2,  Jingmin Zhang3,  Jian Cao2,  Jicai Feng2,  Xiaobin Niu1,  Jianming Bai4,  Junlei Qi2( ),  Peng Gao2,3,5,6( ),  Liping Wang1( ),  Hong Li7
School of Materials and Energy, State Key Laboratory of Electronic Thin Film and Integrated Devices,University of Electronic Science and Technology of China,Chengdu,610054,China;
State Key Laboratory of Advanced Welding and Joining,Harbin Institute of Technology,Harbin,150001,China;
Electron Microscopy Laboratory,School of Physics, Peking University,Beijing,100871,China;
National Synchrotron Light Source Ⅱ,Brookhaven National Laboratory, Upton,New York,11973,USA;
Collaborative Innovation Center of Quantum Matter,Beijing,100871,China;
International Center for Quantum Materials,School of Physics, Peking University,Beijing,100871,China;
Institute of Physics,Chinese Academy of Sciences,Beijing,100190,China;
Keywords:
lithium-ion batteries, scanning transmission electron microscopy, Li-deficient lithium vanadium phosphate, capacity fading, solid electrolyte interphase, electron energy loss spectroscopy
Topics:
CathodesElectron energy levels Electron scatteringElectronsHigh resolution transmission electron microscopyIon batteriesLithiumScanning electron microscopyState BatteriesVanadium compounds
Cite this article:
Chen S, Zou J, Li Y, et al. Atomic-scale structural and chemical evolution of Li3V2(PO4)3 cathode cycled at high voltage window. Nano Research, 2019, 12(7): 1675-1681. https://doi.org/10.1007/s12274-019-2421-9
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Abstract Full text Electronic supplementary material About this article

Here, by using atomically resolved scanning transmission electron microscopy and electron energy loss spectroscopy, we investigate the structural and chemical evolution of Li3V2(PO4)3 (LVP) upon the high-voltage window (3.0–4.8 V). We find that the valence of vanadium gradually increases towards the core corresponding to the formation of electrochemically inactive Li3-xV2(PO4)3 (L3-xVP) phases. These Li-deficient phases exhibit structure distortion with superstructure stripes, likely caused by the migration of the vanadium, which can slow down the lithium ion diffusion or even block the diffusion channels. Such kinetic limitations lead to the formation of Li-deficient phase along with capacity loss. Thus, the LVP continuously losses of electrochemical activity and Li-deficient phases gradually grow from the particle core towards the surface during cycling. After 500 cycles, the thickness of active LVP layer decreases to be ~ 5–20 nm. Moreover, the micromorphology and chemical composition of solid electrolyte interphase (SEI) have been investigated, indicating the thick SEI film also contributes to the capacity loss. The present work reveals the structural and chemical evolution in the cycled electrode materials at an atomic scale, which is essential to understand the voltage fading and capacity decaying of LVP cathode.


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Abstract
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Electronic supplementary material
About this article

Atomic-scale structural and chemical evolution of Li3V2(PO4)3 cathode cycled at high voltage window

Show Author's information Shulin Chen1,2,3, Jian Zou1, Yuehui Li3, Ning Li3, Mei Wu3, Jinghuang Lin2, Jingmin Zhang3, Jian Cao2, Jicai Feng2, Xiaobin Niu1, Jianming Bai4, Junlei Qi2( ), Peng Gao2,3,5,6( ), Liping Wang1( ), Hong Li7
School of Materials and Energy, State Key Laboratory of Electronic Thin Film and Integrated Devices,University of Electronic Science and Technology of China,Chengdu,610054,China;
State Key Laboratory of Advanced Welding and Joining,Harbin Institute of Technology,Harbin,150001,China;
Electron Microscopy Laboratory,School of Physics, Peking University,Beijing,100871,China;
National Synchrotron Light Source Ⅱ,Brookhaven National Laboratory, Upton,New York,11973,USA;
Collaborative Innovation Center of Quantum Matter,Beijing,100871,China;
International Center for Quantum Materials,School of Physics, Peking University,Beijing,100871,China;
Institute of Physics,Chinese Academy of Sciences,Beijing,100190,China;

Abstract

Here, by using atomically resolved scanning transmission electron microscopy and electron energy loss spectroscopy, we investigate the structural and chemical evolution of Li3V2(PO4)3 (LVP) upon the high-voltage window (3.0–4.8 V). We find that the valence of vanadium gradually increases towards the core corresponding to the formation of electrochemically inactive Li3-xV2(PO4)3 (L3-xVP) phases. These Li-deficient phases exhibit structure distortion with superstructure stripes, likely caused by the migration of the vanadium, which can slow down the lithium ion diffusion or even block the diffusion channels. Such kinetic limitations lead to the formation of Li-deficient phase along with capacity loss. Thus, the LVP continuously losses of electrochemical activity and Li-deficient phases gradually grow from the particle core towards the surface during cycling. After 500 cycles, the thickness of active LVP layer decreases to be ~ 5–20 nm. Moreover, the micromorphology and chemical composition of solid electrolyte interphase (SEI) have been investigated, indicating the thick SEI film also contributes to the capacity loss. The present work reveals the structural and chemical evolution in the cycled electrode materials at an atomic scale, which is essential to understand the voltage fading and capacity decaying of LVP cathode.

Keywords: lithium-ion batteries, scanning transmission electron microscopy, Li-deficient lithium vanadium phosphate, capacity fading, solid electrolyte interphase, electron energy loss spectroscopy

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Publication history
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Acknowledgements

Publication history

Received: 06 February 2019
Revised: 14 April 2019
Accepted: 21 April 2019
Published: 08 May 2019
Issue date: July 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

The work was supported by the National Natural Science Foundation of China (Nos. 51502032, 51575135, U1537206, 51502007, and 51672007), the National Basic Research Program of China (Nos. 2016YFA0300804 and 2016YFA0300903], and "2011 Program" Peking-Tsinghua-IOP Collaborative Innovation Center of Quantum Matter. We gratefully acknowledge Electron Microscopy Laboratory in Peking University for the use of Cs corrected electron microscope.

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