Manipulating Phase Stability and Kinetics in Prussian Blue Cathode via Entropy Engineering and d10 Cation Incorporation for Potassium-Ion Batteries.

IF 9.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Nano Letters Pub Date : 2025-10-05 DOI:10.1021/acs.nanolett.5c04114

Honglin Huang,Shuangyan Qiao,Benhui Lv,Hua Kun Liu,Shi Xue Dou,Shaokun Chong

{"title":"Manipulating Phase Stability and Kinetics in Prussian Blue Cathode via Entropy Engineering and d10 Cation Incorporation for Potassium-Ion Batteries.","authors":"Honglin Huang,Shuangyan Qiao,Benhui Lv,Hua Kun Liu,Shi Xue Dou,Shaokun Chong","doi":"10.1021/acs.nanolett.5c04114","DOIUrl":null,"url":null,"abstract":"Phase transition and [Fe(CN)6]4- defects seriously limit electrochemical performance of Prussian blue analogue (PBA) cathodes for potassium-ion batteries (PIBs). Herein, entropy engineering and d10 cation incorporation are utilized to construct a medium-entropy PBA, K1.23Fe0.42Mn0.45Sn0.13[Fe(CN)6]0.94·1.35H2O (KFMSHCF), as the cathode material for PIBs. Entropy-induced cation disorder markedly suppresses anion vacancies, while the entropy stabilization effect and Sn2+ with a d10 configuration stabilize local coordination environments. High configurational entropy boosts KFMSHCF to exhibit reduced band gap and low K-ion diffusion barrier, thereby ensuring excellent electrochemical kinetic. KFMSHCF undergoes a zero-strain solid-solution mechanism using Fe, Mn and Sn ions as redox centers for charge compensation. Therefore, KFMSHCF delivers a high initial energy density of 364.2 Wh·kg-1, remarkable cycling stability with a capacity retention of 82.1% after 100 cycles and long lifespan over 300 cycles, and significantly enhanced rate capability. The fabricated high-energy-density K-ion full batteries achieve ultralong lifespan over 2500 cycles with an ultralow capacity-decay-rate of 0.017% per cycle.","PeriodicalId":53,"journal":{"name":"Nano Letters","volume":"1 1","pages":""},"PeriodicalIF":9.1000,"publicationDate":"2025-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nano Letters","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acs.nanolett.5c04114","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

Abstract

Phase transition and [Fe(CN)6]4- defects seriously limit electrochemical performance of Prussian blue analogue (PBA) cathodes for potassium-ion batteries (PIBs). Herein, entropy engineering and d10 cation incorporation are utilized to construct a medium-entropy PBA, K1.23Fe0.42Mn0.45Sn0.13[Fe(CN)6]0.94·1.35H2O (KFMSHCF), as the cathode material for PIBs. Entropy-induced cation disorder markedly suppresses anion vacancies, while the entropy stabilization effect and Sn2+ with a d10 configuration stabilize local coordination environments. High configurational entropy boosts KFMSHCF to exhibit reduced band gap and low K-ion diffusion barrier, thereby ensuring excellent electrochemical kinetic. KFMSHCF undergoes a zero-strain solid-solution mechanism using Fe, Mn and Sn ions as redox centers for charge compensation. Therefore, KFMSHCF delivers a high initial energy density of 364.2 Wh·kg-1, remarkable cycling stability with a capacity retention of 82.1% after 100 cycles and long lifespan over 300 cycles, and significantly enhanced rate capability. The fabricated high-energy-density K-ion full batteries achieve ultralong lifespan over 2500 cycles with an ultralow capacity-decay-rate of 0.017% per cycle.

查看原文本刊更多论文

通过熵工程和钾离子电池的d10阳离子掺入来控制普鲁士蓝阴极的相稳定性和动力学。

相变和[Fe(CN)6]4-缺陷严重限制了钾离子电池（PIBs）用普鲁士蓝类似物（PBA）阴极的电化学性能。本文利用熵工程和d10正离子掺入构建了中等熵PBA， K1.23Fe0.42Mn0.45Sn0.13[Fe(CN)6]0.94·1.35H2O (KFMSHCF)，作为PIBs的正极材料。熵诱导的阳离子无序性明显抑制了阴离子空位，而熵稳定效应和d10构型的Sn2+稳定了局部配位环境。高的构型熵使得KFMSHCF呈现出更小的带隙和更低的k离子扩散势垒，从而保证了优异的电化学动力学。KFMSHCF以Fe、Mn和Sn离子为氧化还原中心进行电荷补偿，呈现零应变固溶机制。因此，KFMSHCF具有364.2 Wh·kg-1的高初始能量密度，出色的循环稳定性，100次循环后容量保持率为82.1%，超过300次循环的长寿命，并显着提高了倍率能力。制备的高能量密度k离子全电池实现了超过2500次循环的超长寿命，每循环的超低容量衰减率为0.017%。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Nano Letters 工程技术-材料科学：综合

CiteScore

16.80

自引率

2.80%

发文量

1182

审稿时长

1.4 months

期刊介绍： Nano Letters serves as a dynamic platform for promptly disseminating original results in fundamental, applied, and emerging research across all facets of nanoscience and nanotechnology. A pivotal criterion for inclusion within Nano Letters is the convergence of at least two different areas or disciplines, ensuring a rich interdisciplinary scope. The journal is dedicated to fostering exploration in diverse areas, including: - Experimental and theoretical findings on physical, chemical, and biological phenomena at the nanoscale - Synthesis, characterization, and processing of organic, inorganic, polymer, and hybrid nanomaterials through physical, chemical, and biological methodologies - Modeling and simulation of synthetic, assembly, and interaction processes - Realization of integrated nanostructures and nano-engineered devices exhibiting advanced performance - Applications of nanoscale materials in living and environmental systems Nano Letters is committed to advancing and showcasing groundbreaking research that intersects various domains, fostering innovation and collaboration in the ever-evolving field of nanoscience and nanotechnology.