Unveiling the Influence of Cyanogen Vacancies in Prussian Blue for Sodium‐ion Batteries

X Xiang Gao L Longlong Guo S Shangjun Zhang (Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China) H Haoquan Li (Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China) N Nuo Chen Y Yuehang Han (Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China) B Bohui He (Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China) P Peiying Ma (Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China) W Wensheng Gao Y Yongxiao Bai (Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China)

Abstract

Abstract Prussian blue (PB), recognized as a promising cathode material, has gained significant attention for sodium‐ion batteries due to its high theoretical energy density, low cost, and ease of synthesis. However, the influence of anion vacancies on the stability of the PB framework remains controversial, impeding a comprehensive grasp of their precise role in electrochemical performance and the controlled synthesis of PB with smaller anionic vacancies remains challenging due to the limitations inherent in current synthesis strategies. Herein, we present an anion complexation method to synthesize PB materials with tunable cyanide vacancy concentrations. Furthermore, we propose a vacancy‐driven mechanism that promotes spin transitions coupled with lattice bending, which are more reversible at low‐spin Fe sites, leading to excellent low‐spin stability and the design of materials with outstanding electrochemical performance. This anion complexation method not only provides a novel synthetic pathway for PB materials but also advances the understanding of the composition‐structure‐property relationships between cyanide vacancy configurations and spin transition mechanism, highlighting its potential for future energy storage applications.

Article Details

Volume / Issue Vol. 64, Issue 35
Published August 25, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (10)

X

Xiang Gao

L

Longlong Guo

S

Shangjun Zhang

Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China

H

Haoquan Li

Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China

N

Nuo Chen

Y

Yuehang Han

Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China

B

Bohui He

Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China

P

Peiying Ma

Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China

W

Wensheng Gao

Y

Yongxiao Bai

Institute of Soft‐Matter and Advanced Functional Materials Carbon New Materials Industry Technology Center of Gansu Province Key Laboratory of Special Function Materials and Structure Design of Ministry of Education School of Materials and Energy Lanzhou University Lanzhou City Gansu Province China