山东大学徐立强课题组取得一项新突破。他们的研究实现了超长时宽温程钠离子电池普鲁士蓝类似物的理性设计。这一研究成果于2025年1月14日发表在国际顶尖学术期刊《美国化学会杂志》上。

设计具有优化的协同双金属反应中心的普鲁士蓝类似物（PBA）阴极，是设计高能钠离子电池（SIB）的典型策略。然而，这些阴极通常存在容量衰减快和反应动力学缓慢的问题。为了解决上述问题，该研究采用“酸辅助合成”的方法制备了一系列，早期过渡金属(ETM) -晚期过渡金属(LTM)基PBA （Fe-VO、Fe-TiO、Fe-ZrO、Co-VO和Fe-Co-VO）正极材料。

作为范例，FeVO-PBA （FV）提供了卓越的倍率能力（分别在0.5℃和100℃下为148.9和56.1 mAh/g），在30,000次循环中具有卓越的循环稳定性，高能量密度（全电池为259.7 Wh/kg）和宽工作温度范围(60 - 80°C)。

原位/非原位技术和密度泛函理论计算揭示了，FeVO-PBA阴极在循环过程中的准零应变和多电子氧化还原机制，支持其较高的比容量和稳定的循环。Fe和V之间的d-d电子补偿效应增强了氧化还原反应的可逆性和动力学，同时提高了FeVO-PBA阴极的电子导电性和结构稳定性。本研究为合理设计具有双金属反应中心的高性能SIB正极材料，开辟了新的道路。

附：英文原文

Title: Rational Design of Prussian Blue Analogues for Ultralong and Wide-Temperature-Range Sodium-Ion Batteries

Author: Zhongxin Jing, Lingtong Kong, Muhammad Mamoor, Lu Wang, Bo Zhang, Bin Wang, Yanjun Zhai, Fengbo Wang, Guangmeng Qu, Yueyue Kong, Dedong Wang, Liqiang Xu

Issue&Volume: January 14, 2025

Abstract: Architecting Prussian blue analogue (PBA) cathodes with optimized synergistic bimetallic reaction centers is a paradigmatic strategy for devising high-energy sodium-ion batteries (SIBs); however, these cathodes usually suffer from fast capacity fading and sluggish reaction kinetics. To alleviate the above problems, herein, a series of early transition metal (ETM)–late transition metal (LTM)-based PBA (Fe-VO, Fe-TiO, Fe-ZrO, Co-VO, and Fe-Co-VO) cathode materials have been conveniently fabricated via an “acid-assisted synthesis” strategy. As a paradigm, the FeVO-PBA (FV) delivers a superb rate capability (148.9 and 56.1 mAh/g under 0.5 and 100 C, respectively), remarkable cycling stability over 30,000 cycles, high energy density (259.7 Wh/kg for the full cell), and a wide operation-temperature range (60–80 °C). In situ/ex situ techniques and density functional theory calculations reveal the quasi-zero-strain and multielectron redox mechanisms of the FeVO-PBA cathode during cycling, supporting its higher specific capacity and stable cycling. It is considered that the d–d electron compensation effect between Fe and V enhanced the reversibility and kinetics of redox reactions and simultaneously improved the electronic conductivity and structural stability of the FeVO-PBA cathode. This work may pave a new way for the rational design of high-performance cathode materials with bimetallic reaction centers for SIBs.

DOI: 10.1021/jacs.4c16031

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c16031