Manipulating the Dispersed Domain of Pinning Dopants in Layered Oxide Cathodes for Sodium‐Ion Batteries

Z Ziheng Zhang M Machuan Hou (State Key Laboratory of Advanced Chemical Power Sources Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Academy of Advanced Interdisciplinary Studies College of Chemistry Nankai University Tianjin China) J Jiangtao Yu (Frontiers Science Center for New Organic Matter, State Key Laboratory of Advanced Chemical Power Sources, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Academy of Advanced Inter Disciplinary Studies, College of Chemistry) P Peixin Jiao (Frontiers Science Center for New Organic Matter, Key Laboratory of Advanced Energy Materials Chemistry (MOE), College of Chemistry) J Jing Liu Y Yanxia Deng (State Key Laboratory of Advanced Chemical Power Sources Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Academy of Advanced Interdisciplinary Studies College of Chemistry Nankai University Tianjin China) M Meihong Che (State Key Laboratory of Advanced Chemical Power Sources Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Academy of Advanced Interdisciplinary Studies College of Chemistry Nankai University Tianjin China) J Jiahua Zhao Z Zixin Liang (School of Energy and Power Engineering Nanjing University of Science and Technology Nanjing China) L Lunhua He L Limin Zhou (School of Energy and Power Engineering) Z Zhenhua Yan (Frontiers Science Center for New Organic Matter, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), State Key Laboratory of Advanced Chemical Power Sources, College of Chemistry) J Jun Chen K Kai Zhang

Abstract

ABSTRACT Layered oxide cathodes are primary candidates for high‐performance sodium‐ion batteries, which often suffer from structural degradation during deep Na + (de)intercalation processes. Incorporating electrochemically inactive cations into the transition metal (TM) layers has emerged as a mainstream strategy to enhance structural stability through the so‐called pinning effect. However, the microstructural heterogeneity of inactive cations within the TM layers and the spatial extent of their influence remain poorly understood. In this work, we regulate the pinning domain by modulating configurational entropy of inactive ions (S config ‐I), thereby promoting their dispersion and maximizing the spatial extent of the pinning effect. Additionally, we establish a correlation between S config ‐I and local structural fluctuations using quantitative experimental analyses. Compared with samples lacking sufficient pinning domains, the sample with 21% S config ‐I (denoted as S‐I‐21%) exhibits markedly improved structural homogeneity and optimally dispersed pinning dopants. Accordingly, S‐I‐21% delivers a high reversible capacity of 145 mAh g −1 and maintains ∼80% capacity retention after 500 cycles within a wide voltage window (2.0−4.3 V). These findings highlight the effect domain of dopants and their role in regulating structural chemistry, providing design principles for robust layered cathodes.

Article Details

Volume / Issue Vol. 65, Issue 11
Published March 09, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (14)

Z

Ziheng Zhang

M

Machuan Hou

State Key Laboratory of Advanced Chemical Power Sources Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Academy of Advanced Interdisciplinary Studies College of Chemistry Nankai University Tianjin China

J

Jiangtao Yu

Frontiers Science Center for New Organic Matter, State Key Laboratory of Advanced Chemical Power Sources, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Academy of Advanced Inter Disciplinary Studies, College of Chemistry

P

Peixin Jiao

Frontiers Science Center for New Organic Matter, Key Laboratory of Advanced Energy Materials Chemistry (MOE), College of Chemistry

J

Jing Liu

Y

Yanxia Deng

State Key Laboratory of Advanced Chemical Power Sources Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Academy of Advanced Interdisciplinary Studies College of Chemistry Nankai University Tianjin China

M

Meihong Che

State Key Laboratory of Advanced Chemical Power Sources Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Academy of Advanced Interdisciplinary Studies College of Chemistry Nankai University Tianjin China

J

Jiahua Zhao

Z

Zixin Liang

School of Energy and Power Engineering Nanjing University of Science and Technology Nanjing China

L

Lunhua He

L

Limin Zhou

School of Energy and Power Engineering

Z

Zhenhua Yan

Frontiers Science Center for New Organic Matter, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), State Key Laboratory of Advanced Chemical Power Sources, College of Chemistry

J

Jun Chen

K

Kai Zhang