Experimental and theoretical investigation of Na4MnAl(PO4)3 cathode material for sodium-ion batteries

Qianchen Wang; Chen Ling; Jingbo Li; Hongcai Gao; Zongguo Wang; Haibo Jin

doi:10.1016/j.cej.2021.130680

Experimental and theoretical investigation of Na₄MnAl(PO₄)₃ cathode material for sodium-ion batteries

Qianchen Wang, Chen Ling, Jingbo Li^*, Hongcai Gao, Zongguo Wang, Haibo Jin

^*Corresponding author for this work

School of Material Science and Engineering

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

57 Citations (Scopus)

Abstract

Finding appropriate structures of cathode materials is crucial to the development of sodium-ion batteries (SIBs). A novel NASICON-related structure (R-32 space group) of Na₄MnAl(PO₄)₃ is synthesized, which exhibits a high specific capacity (116.8 mAh g⁻¹) with two voltage plateaus of ~ 3.56 V and ~ 4.10 V for Mn³⁺/Mn²⁺ and Mn⁴⁺/Mn³⁺ redox couples, respectively. The sodium ion storage mechanism and diffusion mechanism are investigated by ex-situ XRD and ex-situ XPS, with the aid of first principle calculations. Both two-phase and solid solution reactions take place in the charge/discharge process, and the diffusion path along Na(1) ↔ Na(2) ↔ Na(3) is revealed for the first time in NASICON-structured materials. In addition, a voltage plateau of ~ 4.48 V of the Mn⁵⁺/Mn⁴⁺ redox couple is suggested by the DFT calculations in Na₄MnAl(PO₄)₃, which may be more easily accessed than that of other compounds such as Na₃MnTi(PO₄)₃ and Na₃MnZr(PO₄)₃ reported in literature, leaving great potential in elevating the voltage and specific capacity for Na₄MnAl(PO₄)₃ cathode. Because of high theoretical specific capacity, high voltage plateaus and low cost, Na₄MnAl(PO₄)₃ is a strong contender in cathode material for SIBs.

Original language	English
Article number	130680
Journal	Chemical Engineering Journal
Volume	425
DOIs	https://doi.org/10.1016/j.cej.2021.130680
Publication status	Published - 1 Dec 2021

Keywords

Cathode material
Diffusion mechanism
NaMnAl(PO)
R-32 space group
Sodium ion batteries

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10.1016/j.cej.2021.130680

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title = "Experimental and theoretical investigation of Na4MnAl(PO4)3 cathode material for sodium-ion batteries",

abstract = "Finding appropriate structures of cathode materials is crucial to the development of sodium-ion batteries (SIBs). A novel NASICON-related structure (R-32 space group) of Na4MnAl(PO4)3 is synthesized, which exhibits a high specific capacity (116.8 mAh g−1) with two voltage plateaus of ~ 3.56 V and ~ 4.10 V for Mn3+/Mn2+ and Mn4+/Mn3+ redox couples, respectively. The sodium ion storage mechanism and diffusion mechanism are investigated by ex-situ XRD and ex-situ XPS, with the aid of first principle calculations. Both two-phase and solid solution reactions take place in the charge/discharge process, and the diffusion path along Na(1) ↔ Na(2) ↔ Na(3) is revealed for the first time in NASICON-structured materials. In addition, a voltage plateau of ~ 4.48 V of the Mn5+/Mn4+ redox couple is suggested by the DFT calculations in Na4MnAl(PO4)3, which may be more easily accessed than that of other compounds such as Na3MnTi(PO4)3 and Na3MnZr(PO4)3 reported in literature, leaving great potential in elevating the voltage and specific capacity for Na4MnAl(PO4)3 cathode. Because of high theoretical specific capacity, high voltage plateaus and low cost, Na4MnAl(PO4)3 is a strong contender in cathode material for SIBs.",

keywords = "Cathode material, Diffusion mechanism, NaMnAl(PO), R-32 space group, Sodium ion batteries",

author = "Qianchen Wang and Chen Ling and Jingbo Li and Hongcai Gao and Zongguo Wang and Haibo Jin",

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T1 - Experimental and theoretical investigation of Na4MnAl(PO4)3 cathode material for sodium-ion batteries

AU - Wang, Qianchen

AU - Ling, Chen

AU - Li, Jingbo

AU - Gao, Hongcai

AU - Wang, Zongguo

AU - Jin, Haibo

PY - 2021/12/1

Y1 - 2021/12/1

N2 - Finding appropriate structures of cathode materials is crucial to the development of sodium-ion batteries (SIBs). A novel NASICON-related structure (R-32 space group) of Na4MnAl(PO4)3 is synthesized, which exhibits a high specific capacity (116.8 mAh g−1) with two voltage plateaus of ~ 3.56 V and ~ 4.10 V for Mn3+/Mn2+ and Mn4+/Mn3+ redox couples, respectively. The sodium ion storage mechanism and diffusion mechanism are investigated by ex-situ XRD and ex-situ XPS, with the aid of first principle calculations. Both two-phase and solid solution reactions take place in the charge/discharge process, and the diffusion path along Na(1) ↔ Na(2) ↔ Na(3) is revealed for the first time in NASICON-structured materials. In addition, a voltage plateau of ~ 4.48 V of the Mn5+/Mn4+ redox couple is suggested by the DFT calculations in Na4MnAl(PO4)3, which may be more easily accessed than that of other compounds such as Na3MnTi(PO4)3 and Na3MnZr(PO4)3 reported in literature, leaving great potential in elevating the voltage and specific capacity for Na4MnAl(PO4)3 cathode. Because of high theoretical specific capacity, high voltage plateaus and low cost, Na4MnAl(PO4)3 is a strong contender in cathode material for SIBs.

AB - Finding appropriate structures of cathode materials is crucial to the development of sodium-ion batteries (SIBs). A novel NASICON-related structure (R-32 space group) of Na4MnAl(PO4)3 is synthesized, which exhibits a high specific capacity (116.8 mAh g−1) with two voltage plateaus of ~ 3.56 V and ~ 4.10 V for Mn3+/Mn2+ and Mn4+/Mn3+ redox couples, respectively. The sodium ion storage mechanism and diffusion mechanism are investigated by ex-situ XRD and ex-situ XPS, with the aid of first principle calculations. Both two-phase and solid solution reactions take place in the charge/discharge process, and the diffusion path along Na(1) ↔ Na(2) ↔ Na(3) is revealed for the first time in NASICON-structured materials. In addition, a voltage plateau of ~ 4.48 V of the Mn5+/Mn4+ redox couple is suggested by the DFT calculations in Na4MnAl(PO4)3, which may be more easily accessed than that of other compounds such as Na3MnTi(PO4)3 and Na3MnZr(PO4)3 reported in literature, leaving great potential in elevating the voltage and specific capacity for Na4MnAl(PO4)3 cathode. Because of high theoretical specific capacity, high voltage plateaus and low cost, Na4MnAl(PO4)3 is a strong contender in cathode material for SIBs.

KW - Cathode material

KW - Diffusion mechanism

KW - NaMnAl(PO)

KW - R-32 space group

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Experimental and theoretical investigation of Na₄MnAl(PO₄)₃ cathode material for sodium-ion batteries

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