Ligand Field Electronic State Regulation of Monoclinic Prussian White Toward Highly Stable Sodium‐Ion Batteries
Abstract
Abstract Manganese hexacyanoferrate (MnHCF) has a high output voltage and is expected to be a promising cathode material for high energy density sodium‐ion batteries (SIBs). However, the capacity decay problem caused by the Jahn–Teller effect of high‐spin Mn 3+ restricts its use in sodium‐ion batteries. In this study, an elemental modulation strategy is proposed to regulate the electronic state of the ligand field by introducing the nickel element, which can keep the Mn in a low‐spin configuration during cycling to inhibit the Jahn–Teller aberration of MnHCF. The nickel‐doped MnHCF (NLS2‐PW) with low‐spin electronic state inhibits the disproportionation and dissolution process of Mn 3+ and thus exhibits excellent cycling stability, and its capacity retention is close to 80% after 600 cycles at 2 C with a reduction of the Mn dissolution by ≈70%. Combined with theoretical calculations, it is confirmed that the distortion of the MnN 6 octahedron in NLS2‐PW is reduced significantly, and the tetragonal phase transition caused by the Jahn–Teller effect during the electrochemical process is also effectively suppressed. This work demonstrates an efficient modulation strategy to enhance the performance of the Prussian blue analog cathode of sodium‐ion batteries, being favorable for the design and optimization of relevant PB analogues for SIB applications.
Article Details
Authors (14)
Kang‐Rui Ren
Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province School of Resources and Materials Northeastern University at Qinhuangdao Qinhuangdao 066004 P. R. China
Lang Chen
Collaborative Innovation Center for Statistical Data Engineering, Technology and Application School of Statistics and Mathematics, Zhejiang Gongshang University
Chao‐Zhi Liu
Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province School of Resources and Materials Northeastern University at Qinhuangdao Qinhuangdao 066004 P. R. China
Yue Tian
Xin‐Yi Leng
Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province School of Resources and Materials Northeastern University at Qinhuangdao Qinhuangdao 066004 P. R. China
Ming‐Na Jiang
Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province School of Resources and Materials Northeastern University at Qinhuangdao Qinhuangdao 066004 P. R. China
Zhuo Han
Guan‐You Xiao
Shenzhen Geim Graphene Center Tsinghua Shenzhen International Graduate School Tsinghua University Shenzhen 518055 P. R. China
Guang‐Ning Xu
Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province School of Resources and Materials Northeastern University at Qinhuangdao Qinhuangdao 066004 P. R. China
Zhan Yu
Peng‐Fei Wang
Center of Nanomaterials for Renewable Energy State Key Laboratory of Electrical Insulation and Power Equipment School of Electrical Engineering Xi'an Jiaotong University Xi'an Shaanxi P.R. China
Ying Xie
Yan‐Bing He
Institute of Materials Research Tsinghua Shenzhen International Graduate School Tsinghua University Shenzhen Guangdong 518055 P.R. China
Ting‐Feng Yi
Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province, School of Resources and Materials Northeastern University at Qinhuangdao Qinhuangdao Hebei P. R. China