Reversible multielectron redox in NASICON cathode with high energy density for low-temperature sodium-ion batteries

Chen Sun; Yongjie Zhao; Qing Ni; Zheng Sun; Xuanyi Yuan; Jingbo Li; Haibo Jin

doi:10.1016/j.ensm.2022.04.025

Reversible multielectron redox in NASICON cathode with high energy density for low-temperature sodium-ion batteries

Chen Sun, Yongjie Zhao^*, Qing Ni, Zheng Sun, Xuanyi Yuan, Jingbo Li, Haibo Jin

^*Corresponding author for this work

School of Material Science and Engineering

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

66 Citations (Scopus)

Abstract

The NASICON-type Na₃V₂(PO₄)₃ cathode based on vanadium multiple redox is particularly attractive for large-scale sodium-ion battery application. In this work, it was found that the reversible redox of V⁴⁺/V⁵⁺ can be activated by replacing a part of V³⁺ with Al³⁺, obtaining Na₃V_1.5Al_0.5(PO₄)₃ with typical NASICON phase structure and offering a reversible specific capacity of 163 mAh g⁻¹ through a three-electron redox reaction with a small volume change (2.62%). The most surprising thing is that in addition to favorable room temperature electrochemical performance, Na₃V_1.5Al_0.5(PO₄)₃ also exhibits a superior low temperature (-20 °C) cycling stability with a capacity retention of 98.9% after 1000 cycles at 5 C. Thin and conformal CEI film as well as stable phase structure across a broad temperature range are responsible for this superior electrochemical property. A Na⁺ storage mechanism consisting of two-phase and solid-solution electrochemical reactions for Na₃V_1.5Al_0.5(PO₄)₃ cathode is elucidated via ex-situ XRD structural analysis. DFT calculations indicate that Al³⁺ substitution could manipulate the localized electronic state and strengthen the oxygen ligand skeleton in the NASICON matrix. Hence, the Na₃V_1.5Al_0.5(PO₄)₃ cathode renders a slight lattice variation upon the repeated desodiation and sodiation and enhanced Na⁺ diffusion rate along with low charge transfer resistance.

Original language	English
Pages (from-to)	291-298
Number of pages	8
Journal	Energy Storage Materials
Volume	49
DOIs	https://doi.org/10.1016/j.ensm.2022.04.025
Publication status	Published - Aug 2022

Keywords

Cathode
Low temperature
Multielectron reaction
NASICON

UN SDGs

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

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10.1016/j.ensm.2022.04.025

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@article{ce3139b7122a4d0086ff2bed075aaa1e,

title = "Reversible multielectron redox in NASICON cathode with high energy density for low-temperature sodium-ion batteries",

abstract = "The NASICON-type Na3V2(PO4)3 cathode based on vanadium multiple redox is particularly attractive for large-scale sodium-ion battery application. In this work, it was found that the reversible redox of V4+/V5+ can be activated by replacing a part of V3+ with Al3+, obtaining Na3V1.5Al0.5(PO4)3 with typical NASICON phase structure and offering a reversible specific capacity of 163 mAh g−1 through a three-electron redox reaction with a small volume change (2.62%). The most surprising thing is that in addition to favorable room temperature electrochemical performance, Na3V1.5Al0.5(PO4)3 also exhibits a superior low temperature (-20 °C) cycling stability with a capacity retention of 98.9% after 1000 cycles at 5 C. Thin and conformal CEI film as well as stable phase structure across a broad temperature range are responsible for this superior electrochemical property. A Na+ storage mechanism consisting of two-phase and solid-solution electrochemical reactions for Na3V1.5Al0.5(PO4)3 cathode is elucidated via ex-situ XRD structural analysis. DFT calculations indicate that Al3+ substitution could manipulate the localized electronic state and strengthen the oxygen ligand skeleton in the NASICON matrix. Hence, the Na3V1.5Al0.5(PO4)3 cathode renders a slight lattice variation upon the repeated desodiation and sodiation and enhanced Na+ diffusion rate along with low charge transfer resistance.",

keywords = "Cathode, Low temperature, Multielectron reaction, NASICON",

author = "Chen Sun and Yongjie Zhao and Qing Ni and Zheng Sun and Xuanyi Yuan and Jingbo Li and Haibo Jin",

note = "Publisher Copyright: {\textcopyright} 2022",

year = "2022",

month = aug,

doi = "10.1016/j.ensm.2022.04.025",

language = "English",

volume = "49",

pages = "291--298",

journal = "Energy Storage Materials",

issn = "2405-8297",

publisher = "Elsevier B.V.",

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T1 - Reversible multielectron redox in NASICON cathode with high energy density for low-temperature sodium-ion batteries

AU - Sun, Chen

AU - Zhao, Yongjie

AU - Ni, Qing

AU - Sun, Zheng

AU - Yuan, Xuanyi

AU - Li, Jingbo

AU - Jin, Haibo

PY - 2022/8

Y1 - 2022/8

N2 - The NASICON-type Na3V2(PO4)3 cathode based on vanadium multiple redox is particularly attractive for large-scale sodium-ion battery application. In this work, it was found that the reversible redox of V4+/V5+ can be activated by replacing a part of V3+ with Al3+, obtaining Na3V1.5Al0.5(PO4)3 with typical NASICON phase structure and offering a reversible specific capacity of 163 mAh g−1 through a three-electron redox reaction with a small volume change (2.62%). The most surprising thing is that in addition to favorable room temperature electrochemical performance, Na3V1.5Al0.5(PO4)3 also exhibits a superior low temperature (-20 °C) cycling stability with a capacity retention of 98.9% after 1000 cycles at 5 C. Thin and conformal CEI film as well as stable phase structure across a broad temperature range are responsible for this superior electrochemical property. A Na+ storage mechanism consisting of two-phase and solid-solution electrochemical reactions for Na3V1.5Al0.5(PO4)3 cathode is elucidated via ex-situ XRD structural analysis. DFT calculations indicate that Al3+ substitution could manipulate the localized electronic state and strengthen the oxygen ligand skeleton in the NASICON matrix. Hence, the Na3V1.5Al0.5(PO4)3 cathode renders a slight lattice variation upon the repeated desodiation and sodiation and enhanced Na+ diffusion rate along with low charge transfer resistance.

AB - The NASICON-type Na3V2(PO4)3 cathode based on vanadium multiple redox is particularly attractive for large-scale sodium-ion battery application. In this work, it was found that the reversible redox of V4+/V5+ can be activated by replacing a part of V3+ with Al3+, obtaining Na3V1.5Al0.5(PO4)3 with typical NASICON phase structure and offering a reversible specific capacity of 163 mAh g−1 through a three-electron redox reaction with a small volume change (2.62%). The most surprising thing is that in addition to favorable room temperature electrochemical performance, Na3V1.5Al0.5(PO4)3 also exhibits a superior low temperature (-20 °C) cycling stability with a capacity retention of 98.9% after 1000 cycles at 5 C. Thin and conformal CEI film as well as stable phase structure across a broad temperature range are responsible for this superior electrochemical property. A Na+ storage mechanism consisting of two-phase and solid-solution electrochemical reactions for Na3V1.5Al0.5(PO4)3 cathode is elucidated via ex-situ XRD structural analysis. DFT calculations indicate that Al3+ substitution could manipulate the localized electronic state and strengthen the oxygen ligand skeleton in the NASICON matrix. Hence, the Na3V1.5Al0.5(PO4)3 cathode renders a slight lattice variation upon the repeated desodiation and sodiation and enhanced Na+ diffusion rate along with low charge transfer resistance.

KW - Cathode

KW - Low temperature

KW - Multielectron reaction

KW - NASICON

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M3 - Article

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SN - 2405-8297

VL - 49

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EP - 298

JO - Energy Storage Materials

JF - Energy Storage Materials

ER -

Reversible multielectron redox in NASICON cathode with high energy density for low-temperature sodium-ion batteries

Abstract

Keywords

UN SDGs

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