{"title":"High-Resolution 6Li Solid-State Nuclear\u0000Magnetic Resonance Reveals Hidden Lithium Dynamics in All-Solid-State\u0000Cathodes","authors":"Houyi Liu,Bao Zhang,Yuhao Duan,Jiuwei Lei,Wen Yin,Wei Xia,Hongzhang Zhang,Kuizhi Chen,Xiaofei Yang,Guangjin Hou,Xianfeng Li","doi":"10.1021/jacs.6c17473","DOIUrl":"https://doi.org/10.1021/jacs.6c17473","url":null,"abstract":"Abstract The decisive chemistry of iron-based halide cathodes─where lithium resides, how it evolves, and how disorder governs multielectron redox─has remained largely inaccessible, limiting the rational design of catholyte-free composite cathodes in all-solid-state lithium batteries. Here we make the lithium sublattice directly visible in paramagnetic LiFeCl3 using a 6Li solid-state NMR strategy combining high isotopic enrichment, optimized acquisition, and variable-temperature control. This method resolves and quantifies three Li+ environments, revealing that local Li/Fe disorder drives in-place Fe2+ reduction as the root cause of highly reversible intercalation-conversion chemistry. It further uncovers trace irreversible Fe0 species invisible to conventional spectroscopic and imaging techniques. Guided by this hidden degradation signature, optimization of the voltage window enables 85.9% capacity retention after 500 cycles with a 16.3% energy-density penalty, whereas full-depth cycling retains 68.6% after 100 cycles. Our work establishes lithium-resolved NMR as a platform linking disorder, hidden redox, and reversibility in paramagnetic cathodes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"42 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}