六氰高铁酸钠阴极在钠离子电池中的降解机理研究

IF 30.8 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Junyi Dai, Jiahao Li, Fangxin Ling, Yu Yao, Yanru Wang, Mingze Ma, Jian Feng, Jun Xia, Yinbo Zhu, Hai Yang, Xianhong Rui, Hengan Wu and Yan Yu
{"title":"六氰高铁酸钠阴极在钠离子电池中的降解机理研究","authors":"Junyi Dai, Jiahao Li, Fangxin Ling, Yu Yao, Yanru Wang, Mingze Ma, Jian Feng, Jun Xia, Yinbo Zhu, Hai Yang, Xianhong Rui, Hengan Wu and Yan Yu","doi":"10.1039/D5EE02117K","DOIUrl":null,"url":null,"abstract":"<p >Sodium iron hexacyanoferrates (Na<small><sub>2</sub></small>FeFe(CN)<small><sub>6</sub></small>) are considered among the most promising cathode materials for sodium ion batteries due to their high theoretical energy density and low cost. However, structural Fe(CN)<small><sub>6</sub></small><small><sup>4−</sup></small> vacancies seriously impair structure stability and deteriorate electrochemical performance. So far, the mechanisms by which Fe(CN)<small><sub>6</sub></small><small><sup>4−</sup></small> vacancies cause performance degradation and ultimately result in material failure have remained unclear, leading to persistent controversies in this field. Herein, we systematically investigate the degradation mechanisms induced by Fe(CN)<small><sub>6</sub></small><small><sup>4−</sup></small> vacancies from experimental and theoretical perspectives. A defective Na<small><sub>2</sub></small>FeFe(CN)<small><sub>6</sub></small> cathode exhibits more hysteretic low-spin iron reaction kinetics, especially during charge transfer and ion diffusion. Cryo-electron microscopy reveals that interfacial side reactions triggered by Fe(CN)<small><sub>6</sub></small><small><sup>4−</sup></small> vacancies during electrochemical cycling produce excessive Na<small><sub>2</sub></small>CO<small><sub>3</sub></small> and NaF byproducts, which deplete electrochemically active Na<small><sup>+</sup></small> within defective structures, causing electrochemical failure of high-spin Fe–N interactions and ultimately leading to poor structural stability. Importantly, pouch full cells (71% retention after 650 cycles) and all-solid-state batteries (82% retention after 500 cycles) fabricated from industrial-scale low-defect Na<small><sub>2</sub></small>FeFe(CN)<small><sub>6</sub></small> cathodes exhibit excellent cycling stability. This work offers valuable mechanistic insights into vacancy-induced degradation of Na<small><sub>2</sub></small>FeFe(CN)<small><sub>6</sub></small> cathodes and contributes to the advancement of practical sodium storage cathode materials.</p>","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":" 19","pages":" 8791-8802"},"PeriodicalIF":30.8000,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unraveling the degradation mechanism of sodium iron hexacyanoferrate cathodes in sodium ion batteries\",\"authors\":\"Junyi Dai, Jiahao Li, Fangxin Ling, Yu Yao, Yanru Wang, Mingze Ma, Jian Feng, Jun Xia, Yinbo Zhu, Hai Yang, Xianhong Rui, Hengan Wu and Yan Yu\",\"doi\":\"10.1039/D5EE02117K\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Sodium iron hexacyanoferrates (Na<small><sub>2</sub></small>FeFe(CN)<small><sub>6</sub></small>) are considered among the most promising cathode materials for sodium ion batteries due to their high theoretical energy density and low cost. However, structural Fe(CN)<small><sub>6</sub></small><small><sup>4−</sup></small> vacancies seriously impair structure stability and deteriorate electrochemical performance. So far, the mechanisms by which Fe(CN)<small><sub>6</sub></small><small><sup>4−</sup></small> vacancies cause performance degradation and ultimately result in material failure have remained unclear, leading to persistent controversies in this field. Herein, we systematically investigate the degradation mechanisms induced by Fe(CN)<small><sub>6</sub></small><small><sup>4−</sup></small> vacancies from experimental and theoretical perspectives. A defective Na<small><sub>2</sub></small>FeFe(CN)<small><sub>6</sub></small> cathode exhibits more hysteretic low-spin iron reaction kinetics, especially during charge transfer and ion diffusion. Cryo-electron microscopy reveals that interfacial side reactions triggered by Fe(CN)<small><sub>6</sub></small><small><sup>4−</sup></small> vacancies during electrochemical cycling produce excessive Na<small><sub>2</sub></small>CO<small><sub>3</sub></small> and NaF byproducts, which deplete electrochemically active Na<small><sup>+</sup></small> within defective structures, causing electrochemical failure of high-spin Fe–N interactions and ultimately leading to poor structural stability. Importantly, pouch full cells (71% retention after 650 cycles) and all-solid-state batteries (82% retention after 500 cycles) fabricated from industrial-scale low-defect Na<small><sub>2</sub></small>FeFe(CN)<small><sub>6</sub></small> cathodes exhibit excellent cycling stability. This work offers valuable mechanistic insights into vacancy-induced degradation of Na<small><sub>2</sub></small>FeFe(CN)<small><sub>6</sub></small> cathodes and contributes to the advancement of practical sodium storage cathode materials.</p>\",\"PeriodicalId\":72,\"journal\":{\"name\":\"Energy & Environmental Science\",\"volume\":\" 19\",\"pages\":\" 8791-8802\"},\"PeriodicalIF\":30.8000,\"publicationDate\":\"2025-08-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy & Environmental Science\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/ee/d5ee02117k\",\"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}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy & Environmental Science","FirstCategoryId":"88","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/ee/d5ee02117k","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

摘要

六氰高铁酸钠(Na2FeFe(CN)6)因其理论能量密度高、成本低而被认为是最有前途的钠离子电池正极材料之一。然而,结构Fe(CN)64-空位严重影响了结构的稳定性和电化学性能。到目前为止,Fe(CN)64-空位导致性能下降并最终导致材料失效的机制尚不清楚,导致该领域的争议持续存在。本文从实验和理论两方面系统研究了Fe(CN)64-空位诱导的降解机制。缺陷的Na2FeFe(CN)6阴极表现出更多的滞后低自旋铁反应动力学,特别是在电荷转移和离子扩散过程中。低温电镜分析表明,在电化学循环过程中,Fe(CN)64-空位引发的界面副反应产生了过量的Na2CO3和NaF副产物,耗尽了缺陷结构内的电化学活性Na+,导致高自旋Fe- n相互作用的电化学失效,最终导致结构稳定性差。重要的是,用工业规模的低缺陷Na2FeFe(CN)6阴极制造的袋状满电池(650次循环后71%的保留率)和全固态电池(500次循环后82%的保留率)表现出优异的循环稳定性。本研究为研究Na2FeFe(CN)6阴极的空位诱导降解提供了有价值的机制见解,并有助于推进实用的钠存储阴极材料。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Unraveling the degradation mechanism of sodium iron hexacyanoferrate cathodes in sodium ion batteries

Unraveling the degradation mechanism of sodium iron hexacyanoferrate cathodes in sodium ion batteries

Sodium iron hexacyanoferrates (Na2FeFe(CN)6) are considered among the most promising cathode materials for sodium ion batteries due to their high theoretical energy density and low cost. However, structural Fe(CN)64− vacancies seriously impair structure stability and deteriorate electrochemical performance. So far, the mechanisms by which Fe(CN)64− vacancies cause performance degradation and ultimately result in material failure have remained unclear, leading to persistent controversies in this field. Herein, we systematically investigate the degradation mechanisms induced by Fe(CN)64− vacancies from experimental and theoretical perspectives. A defective Na2FeFe(CN)6 cathode exhibits more hysteretic low-spin iron reaction kinetics, especially during charge transfer and ion diffusion. Cryo-electron microscopy reveals that interfacial side reactions triggered by Fe(CN)64− vacancies during electrochemical cycling produce excessive Na2CO3 and NaF byproducts, which deplete electrochemically active Na+ within defective structures, causing electrochemical failure of high-spin Fe–N interactions and ultimately leading to poor structural stability. Importantly, pouch full cells (71% retention after 650 cycles) and all-solid-state batteries (82% retention after 500 cycles) fabricated from industrial-scale low-defect Na2FeFe(CN)6 cathodes exhibit excellent cycling stability. This work offers valuable mechanistic insights into vacancy-induced degradation of Na2FeFe(CN)6 cathodes and contributes to the advancement of practical sodium storage cathode materials.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Energy & Environmental Science
Energy & Environmental Science 化学-工程:化工
CiteScore
50.50
自引率
2.20%
发文量
349
审稿时长
2.2 months
期刊介绍: Energy & Environmental Science, a peer-reviewed scientific journal, publishes original research and review articles covering interdisciplinary topics in the (bio)chemical and (bio)physical sciences, as well as chemical engineering disciplines. Published monthly by the Royal Society of Chemistry (RSC), a not-for-profit publisher, Energy & Environmental Science is recognized as a leading journal. It boasts an impressive impact factor of 8.500 as of 2009, ranking 8th among 140 journals in the category "Chemistry, Multidisciplinary," second among 71 journals in "Energy & Fuels," second among 128 journals in "Engineering, Chemical," and first among 181 scientific journals in "Environmental Sciences." Energy & Environmental Science publishes various types of articles, including Research Papers (original scientific work), Review Articles, Perspectives, and Minireviews (feature review-type articles of broad interest), Communications (original scientific work of an urgent nature), Opinions (personal, often speculative viewpoints or hypotheses on current topics), and Analysis Articles (in-depth examination of energy-related issues).
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信