Deciphering the function mechanism of high-valence tantalum doping in O3-types layered cathode for sodium-ion battery

Zixuan Huang; Zhi Long; Cheng Li; Kai Liu; Qingqing Zhang; Shiqiang Liu; Yayu Guo; Weili Sun; Wenyu Mu; Xixi Shi; Hongzhou Zhang; Na Zhang; Dawei Song; Lianqi Zhang

doi:10.1016/j.jechem.2025.08.078

Deciphering the function mechanism of high-valence tantalum doping in O3-types layered cathode for sodium-ion battery

Zixuan Huang
, Zhi Long
, Cheng Li
, Kai Liu
, Qingqing Zhang
, Shiqiang Liu
, Yayu Guo
, Weili Sun
, Wenyu Mu
, Xixi Shi
, Hongzhou Zhang
, Na Zhang
, Dawei Song
, Lianqi Zhang

Powder Diffraction

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

Abstract

O3-types layered cathode materials in sodium-ion batteries (SIBs) suffer from the obvious lattice distortion induced by the complex phase transitions during Na⁺ intercalation/deintercalation process, leading to severe structural collapse and performance degradation. Herein, a series of high valence tantalum (Ta⁵⁺) doped Na(Ni_0.4Fe_0.2Mn_0.4)₁₋_xTa_xO₂ (x = 0/0.0025/0.005/0.01) secondary spherical particles are firstly developed, where Ta⁵⁺ doping enables the refined primary grain with a tightly stacked rod-like morphology. Comprehensive structural analysis via Neutron powder diffraction (NPD) and Synchrotron radiation X-ray diffraction (SXRD) reveals an expanded NaO₂ slab and a reduction in Na site vacancy. The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS), unveiling a partial reduction from Ni³⁺ to Ni²⁺ with Ta⁵⁺ doping. In situ X-ray diffraction (in situ XRD) suggests that the decorated sample undergoes a volume change as low as 0.8 %, in contrast with the pristine one (1.5 %). Thus, the optimized sample with x = 0.005 retains an enhanced capacity retention up to 70.4 % at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg⁻¹ (0.1 C) and with a good capacity retention of 81.0 % at 1 C after 200 cycles in full-cell. Our findings provide new insights into the mechanism of high valence Ta⁵⁺ doping in stabilizing layered oxides cathode materials for SIBs.

Original language	English
Pages (from-to)	742-751
Number of pages	10
Journal	Journal of Energy Chemistry
Volume	112
DOIs	https://doi.org/10.1016/j.jechem.2025.08.078
State	Published - Jan 2026

Funding

This research was supported by the National Natural Science Foundation of China ( 52402298 , 52172224 , 52202228 , 22479112 ), the Science and Technology Correspondent Project of Tianjin ( 24YDTPJC00240 ), Science Research Project of Hebei Education Department ( BJK2022011 ), Central Funds Guiding the Local Science and Technology Development of Hebei Province ( 236Z4404G ), the Beijing Tianjin Hebei Basic Research Cooperation Special Project ( E2024202273 ), and Tianjin Sci. & Tech. Program ( 22YFYSHZ00220 ). The authors appreciate a portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research also employed the resources of BL14B1 beam at Shanghai Synchrotron Radiation Facility (SSRF) (Proposal info: 2023-SSRF-PT-503737 ).

Keywords

Charge compensation mechanism
High valence tantalum doping
Layered cathode materials
Sodium-ion batteries
Structure analysis

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10.1016/j.jechem.2025.08.078

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@article{27e14a05649f467a8ecd2e5b2aabd9ba,

title = "Deciphering the function mechanism of high-valence tantalum doping in O3-types layered cathode for sodium-ion battery",

abstract = "O3-types layered cathode materials in sodium-ion batteries (SIBs) suffer from the obvious lattice distortion induced by the complex phase transitions during Na+ intercalation/deintercalation process, leading to severe structural collapse and performance degradation. Herein, a series of high valence tantalum (Ta5+) doped Na(Ni0.4Fe0.2Mn0.4)1−xTaxO2 (x = 0/0.0025/0.005/0.01) secondary spherical particles are firstly developed, where Ta5+ doping enables the refined primary grain with a tightly stacked rod-like morphology. Comprehensive structural analysis via Neutron powder diffraction (NPD) and Synchrotron radiation X-ray diffraction (SXRD) reveals an expanded NaO2 slab and a reduction in Na site vacancy. The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS), unveiling a partial reduction from Ni3+ to Ni2+ with Ta5+ doping. In situ X-ray diffraction (in situ XRD) suggests that the decorated sample undergoes a volume change as low as 0.8 \%, in contrast with the pristine one (1.5 \%). Thus, the optimized sample with x = 0.005 retains an enhanced capacity retention up to 70.4 \% at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg−1 (0.1 C) and with a good capacity retention of 81.0 \% at 1 C after 200 cycles in full-cell. Our findings provide new insights into the mechanism of high valence Ta5+ doping in stabilizing layered oxides cathode materials for SIBs.",

keywords = "Charge compensation mechanism, High valence tantalum doping, Layered cathode materials, Sodium-ion batteries, Structure analysis",

author = "Zixuan Huang and Zhi Long and Cheng Li and Kai Liu and Qingqing Zhang and Shiqiang Liu and Yayu Guo and Weili Sun and Wenyu Mu and Xixi Shi and Hongzhou Zhang and Na Zhang and Dawei Song and Lianqi Zhang",

note = "Publisher Copyright: {\textcopyright} 2025 Science Press",

year = "2026",

month = jan,

doi = "10.1016/j.jechem.2025.08.078",

language = "English",

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TY - JOUR

T1 - Deciphering the function mechanism of high-valence tantalum doping in O3-types layered cathode for sodium-ion battery

AU - Huang, Zixuan

AU - Long, Zhi

AU - Li, Cheng

AU - Liu, Kai

AU - Zhang, Qingqing

AU - Liu, Shiqiang

AU - Guo, Yayu

AU - Sun, Weili

AU - Mu, Wenyu

AU - Shi, Xixi

AU - Zhang, Hongzhou

AU - Zhang, Na

AU - Song, Dawei

AU - Zhang, Lianqi

PY - 2026/1

Y1 - 2026/1

N2 - O3-types layered cathode materials in sodium-ion batteries (SIBs) suffer from the obvious lattice distortion induced by the complex phase transitions during Na+ intercalation/deintercalation process, leading to severe structural collapse and performance degradation. Herein, a series of high valence tantalum (Ta5+) doped Na(Ni0.4Fe0.2Mn0.4)1−xTaxO2 (x = 0/0.0025/0.005/0.01) secondary spherical particles are firstly developed, where Ta5+ doping enables the refined primary grain with a tightly stacked rod-like morphology. Comprehensive structural analysis via Neutron powder diffraction (NPD) and Synchrotron radiation X-ray diffraction (SXRD) reveals an expanded NaO2 slab and a reduction in Na site vacancy. The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS), unveiling a partial reduction from Ni3+ to Ni2+ with Ta5+ doping. In situ X-ray diffraction (in situ XRD) suggests that the decorated sample undergoes a volume change as low as 0.8 %, in contrast with the pristine one (1.5 %). Thus, the optimized sample with x = 0.005 retains an enhanced capacity retention up to 70.4 % at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg−1 (0.1 C) and with a good capacity retention of 81.0 % at 1 C after 200 cycles in full-cell. Our findings provide new insights into the mechanism of high valence Ta5+ doping in stabilizing layered oxides cathode materials for SIBs.

AB - O3-types layered cathode materials in sodium-ion batteries (SIBs) suffer from the obvious lattice distortion induced by the complex phase transitions during Na+ intercalation/deintercalation process, leading to severe structural collapse and performance degradation. Herein, a series of high valence tantalum (Ta5+) doped Na(Ni0.4Fe0.2Mn0.4)1−xTaxO2 (x = 0/0.0025/0.005/0.01) secondary spherical particles are firstly developed, where Ta5+ doping enables the refined primary grain with a tightly stacked rod-like morphology. Comprehensive structural analysis via Neutron powder diffraction (NPD) and Synchrotron radiation X-ray diffraction (SXRD) reveals an expanded NaO2 slab and a reduction in Na site vacancy. The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS), unveiling a partial reduction from Ni3+ to Ni2+ with Ta5+ doping. In situ X-ray diffraction (in situ XRD) suggests that the decorated sample undergoes a volume change as low as 0.8 %, in contrast with the pristine one (1.5 %). Thus, the optimized sample with x = 0.005 retains an enhanced capacity retention up to 70.4 % at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg−1 (0.1 C) and with a good capacity retention of 81.0 % at 1 C after 200 cycles in full-cell. Our findings provide new insights into the mechanism of high valence Ta5+ doping in stabilizing layered oxides cathode materials for SIBs.

KW - Charge compensation mechanism

KW - High valence tantalum doping

KW - Layered cathode materials

KW - Sodium-ion batteries

KW - Structure analysis

UR - https://www.scopus.com/pages/publications/105016996567

U2 - 10.1016/j.jechem.2025.08.078

DO - 10.1016/j.jechem.2025.08.078

M3 - Article

AN - SCOPUS:105016996567

SN - 2095-4956

VL - 112

SP - 742

EP - 751

JO - Journal of Energy Chemistry

JF - Journal of Energy Chemistry

ER -

Deciphering the function mechanism of high-valence tantalum doping in O3-types layered cathode for sodium-ion battery

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