Orbital modulation to restrain anti-site defects in NASICON cathode for high-performance sodium-ion batteries

Jiandong Zhang; Zhaoshi Yu; Liyuan Tian; Yanbin Zhu; Muqin Wang; Pengkun Gao; Yali Zhang; Naiqing Zhang; Deyu Wang; Yan Shen; Mingkui Wang

doi:10.1088/2752-5724/ae44b2

Orbital modulation to restrain anti-site defects in NASICON cathode for high-performance sodium-ion batteries

Jiandong Zhang
, Zhaoshi Yu
, Liyuan Tian
, Yanbin Zhu
, Muqin Wang
, Pengkun Gao
, Yali Zhang
, Naiqing Zhang
, Deyu Wang
, Yan Shen^*
, Mingkui Wang^*

^*Corresponding author for this work

Huazhong University of Science and Technology
PYTES (Shandong) Energy Technology Co. Ltd.
School of Chemistry and Chemical Engineering, Harbin Institute of Technology
Jianghan University

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

Abstract

Sodium superionic conductor-type Na₃MnTi(PO₄)₃ is a promising cathode for sodium-ion batteries. However, the anti-site defects due to the occupation of Na vacancies by Mn lead to voltage hysteresis and capacity loss. In this study, we present a method for efficient manipulating the e _g orbital of elemental Mn in the Na₃MnTi(PO₄)₃ to enhance the Mn–O covalent interaction. This modulation of the e _g orbital facilitates the electron filling in the Mn (3d–e _g) orbital and strengthens hybridization with the O (2p) orbital, which increases the formation energy of Mn defects and thereby effectively restrains anti-site defects in Na₃MnTi(PO₄)₃. The optimized Na_2.97Li_0.03MnTi(PO₄)₃ cathode delivers a capacity of 115.8 mAh g⁻¹ at 10 C (164.9 mAh g⁻¹ at 0.1 C), while retaining an outstanding capacity retention of 89.2% over 3000 cycles, along with stable cycling characteristics under temperatures ranging from −30 °C to 40 °C. The pouch-type full cell (50 × 35 × 5 mm³) using the Na_2.97Li_0.03MnTi(PO₄)₃ cathode and hard carbon anode further demonstrates its promising application. This study elucidates the anti-site defects suppression mechanism through molecular orbital analysis, offering new perspectives for developing high-performance sodium-ion cathode materials.

Original language	English
Article number	025104
Journal	Materials Futures
Volume	5
Issue number	2
DOIs	https://doi.org/10.1088/2752-5724/ae44b2
State	Published - 1 Jun 2026
Externally published	Yes

Keywords

Mn–O covalency
anti-site defects
electron filling
orbitals modulation
sodium-ion battery

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10.1088/2752-5724/ae44b2

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@article{0c673adeafe542e5bd2293aefb4cd1bb,

title = "Orbital modulation to restrain anti-site defects in NASICON cathode for high-performance sodium-ion batteries",

abstract = "Sodium superionic conductor-type Na3MnTi(PO4)3 is a promising cathode for sodium-ion batteries. However, the anti-site defects due to the occupation of Na vacancies by Mn lead to voltage hysteresis and capacity loss. In this study, we present a method for efficient manipulating the e g orbital of elemental Mn in the Na3MnTi(PO4)3 to enhance the Mn–O covalent interaction. This modulation of the e g orbital facilitates the electron filling in the Mn (3d–e g) orbital and strengthens hybridization with the O (2p) orbital, which increases the formation energy of Mn defects and thereby effectively restrains anti-site defects in Na3MnTi(PO4)3. The optimized Na2.97Li0.03MnTi(PO4)3 cathode delivers a capacity of 115.8 mAh g−1 at 10 C (164.9 mAh g−1 at 0.1 C), while retaining an outstanding capacity retention of 89.2\% over 3000 cycles, along with stable cycling characteristics under temperatures ranging from −30 °C to 40 °C. The pouch-type full cell (50 × 35 × 5 mm3) using the Na2.97Li0.03MnTi(PO4)3 cathode and hard carbon anode further demonstrates its promising application. This study elucidates the anti-site defects suppression mechanism through molecular orbital analysis, offering new perspectives for developing high-performance sodium-ion cathode materials.",

keywords = "Mn–O covalency, anti-site defects, electron filling, orbitals modulation, sodium-ion battery",

author = "Jiandong Zhang and Zhaoshi Yu and Liyuan Tian and Yanbin Zhu and Muqin Wang and Pengkun Gao and Yali Zhang and Naiqing Zhang and Deyu Wang and Yan Shen and Mingkui Wang",

note = "Publisher Copyright: {\textcopyright} 2026 The Author(s). Published by IOP Publishing Ltd on behalf of the Dongguan Institute of Materials Science and Technology, CAS.",

year = "2026",

month = jun,

day = "1",

doi = "10.1088/2752-5724/ae44b2",

language = "英语",

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journal = "Materials Futures",

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TY - JOUR

T1 - Orbital modulation to restrain anti-site defects in NASICON cathode for high-performance sodium-ion batteries

AU - Zhang, Jiandong

AU - Yu, Zhaoshi

AU - Tian, Liyuan

AU - Zhu, Yanbin

AU - Wang, Muqin

AU - Gao, Pengkun

AU - Zhang, Yali

AU - Zhang, Naiqing

AU - Wang, Deyu

AU - Shen, Yan

AU - Wang, Mingkui

PY - 2026/6/1

Y1 - 2026/6/1

N2 - Sodium superionic conductor-type Na3MnTi(PO4)3 is a promising cathode for sodium-ion batteries. However, the anti-site defects due to the occupation of Na vacancies by Mn lead to voltage hysteresis and capacity loss. In this study, we present a method for efficient manipulating the e g orbital of elemental Mn in the Na3MnTi(PO4)3 to enhance the Mn–O covalent interaction. This modulation of the e g orbital facilitates the electron filling in the Mn (3d–e g) orbital and strengthens hybridization with the O (2p) orbital, which increases the formation energy of Mn defects and thereby effectively restrains anti-site defects in Na3MnTi(PO4)3. The optimized Na2.97Li0.03MnTi(PO4)3 cathode delivers a capacity of 115.8 mAh g−1 at 10 C (164.9 mAh g−1 at 0.1 C), while retaining an outstanding capacity retention of 89.2% over 3000 cycles, along with stable cycling characteristics under temperatures ranging from −30 °C to 40 °C. The pouch-type full cell (50 × 35 × 5 mm3) using the Na2.97Li0.03MnTi(PO4)3 cathode and hard carbon anode further demonstrates its promising application. This study elucidates the anti-site defects suppression mechanism through molecular orbital analysis, offering new perspectives for developing high-performance sodium-ion cathode materials.

AB - Sodium superionic conductor-type Na3MnTi(PO4)3 is a promising cathode for sodium-ion batteries. However, the anti-site defects due to the occupation of Na vacancies by Mn lead to voltage hysteresis and capacity loss. In this study, we present a method for efficient manipulating the e g orbital of elemental Mn in the Na3MnTi(PO4)3 to enhance the Mn–O covalent interaction. This modulation of the e g orbital facilitates the electron filling in the Mn (3d–e g) orbital and strengthens hybridization with the O (2p) orbital, which increases the formation energy of Mn defects and thereby effectively restrains anti-site defects in Na3MnTi(PO4)3. The optimized Na2.97Li0.03MnTi(PO4)3 cathode delivers a capacity of 115.8 mAh g−1 at 10 C (164.9 mAh g−1 at 0.1 C), while retaining an outstanding capacity retention of 89.2% over 3000 cycles, along with stable cycling characteristics under temperatures ranging from −30 °C to 40 °C. The pouch-type full cell (50 × 35 × 5 mm3) using the Na2.97Li0.03MnTi(PO4)3 cathode and hard carbon anode further demonstrates its promising application. This study elucidates the anti-site defects suppression mechanism through molecular orbital analysis, offering new perspectives for developing high-performance sodium-ion cathode materials.

KW - Mn–O covalency

KW - anti-site defects

KW - electron filling

KW - orbitals modulation

KW - sodium-ion battery

UR - https://www.scopus.com/pages/publications/105033225569

U2 - 10.1088/2752-5724/ae44b2

DO - 10.1088/2752-5724/ae44b2

M3 - 文章

AN - SCOPUS:105033225569

SN - 2752-5724

VL - 5

JO - Materials Futures

JF - Materials Futures

IS - 2

M1 - 025104

ER -

Orbital modulation to restrain anti-site defects in NASICON cathode for high-performance sodium-ion batteries

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Keywords

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