Liu Shuhui, Yu Haixia, Zhao Yue, Sun Jiaxiang, He Yan, Zhu Dingding, Song Zhonghan, Xu Shucheng, Sun Rizhen, Yang Yunzhi, Tong Sen, Zhang Runyu, Chen Guihuan, Li Qiang
College of Physics, College of Materials Science and Engineering, Weihai Innovation Research Institute, Qingdao University, Qingdao, 266071, China.
Department of Electrical and Computer Engineering & Institute for Quantum Computing, University of Waterloo, Ontario, N2L 3G1, Canada.
Small. 2025 Aug;21(31):e2504893. doi: 10.1002/smll.202504893. Epub 2025 Jun 4.
Prussian blue analogs (PBAs) have garnered considerable attention due to open 3D framework and high theoretical capacity. However, unfavorable phase transitions and inherent low conductivity lead to severe capacity decay and poor rate performance. Herein, the high-entropy (HE) concept is incorporated into PBAs to improve their electrochemical properties. By introducing four inert elements sharing N coordination site with Fe, the high-entropy Na(FeCuNiMgZn)[Fe(CN)] (HEPBA) is constructed. The developed high-entropy Prussian blue analog (HEPBA) exhibits high specific capacity with cyclic stability, stable operation 2000 cycles at 1C, and superior rate performance. Experimental results and theoretical calculations demonstrate that this high-entropy design not only effectively inhibits phase transitions and reinforces structural stability but also activates the redox activity of low-spin-state Fe centers. Simultaneously, it can improve sodium-ion diffusion by optimizing pathways and reducing energy barriers, ultimately enhancing overall performance. This strategy provides an innovative perspective that synergistically optimizes specific capacity, structural stability, and rate performance in PBAs.
普鲁士蓝类似物（PBAs）因其开放的三维框架和高理论容量而备受关注。然而，不利的相变和固有的低电导率导致严重的容量衰减和较差的倍率性能。在此，将高熵（HE）概念引入PBAs以改善其电化学性能。通过引入四个与Fe共享N配位位点的惰性元素，构建了高熵Na(FeCuNiMgZn)[Fe(CN)]（HEPBA）。所开发的高熵普鲁士蓝类似物（HEPBA）表现出高比容量和循环稳定性，在1C下稳定运行2000次循环，且具有优异的倍率性能。实验结果和理论计算表明，这种高熵设计不仅有效地抑制了相变并增强了结构稳定性，还激活了低自旋态Fe中心的氧化还原活性。同时，它可以通过优化路径和降低能垒来改善钠离子扩散，最终提高整体性能。该策略提供了一个创新的视角，可协同优化PBAs中的比容量、结构稳定性和倍率性能。
