doi:10.1039/d5dt00893jengCiria-Ramos, IsabelNeale, Alex R.Hardwick, Laurence J.Juarez-Perez, Emilio J.Gascón, IgnacioHaro, Marta<i>Operando</i> Raman and <i>ex situ</i> characterization of an iron-based conductive MOF as a negative electrode in Li-ion batteriesART-2025-144266An iron-based electrically conductive metal–organic framework (MOF), Fe-HHTP, formed by the coordination of Fe cations and the organic ligand HHTP (2,3,6,7,10,11-hexahydroxytriphenylene), has been synthesized, characterized, and explored as a potential negative electrode for lithium-ion batteries (LIBs). Galvanostatic cycling experiments, with a lower cut-off voltage of 0.1 V vs. Li/Li+, reveal that Fe-HHTP undergoes a significant activation process, resulting in an increase in specific capacity up to 1142 mAh g−1 after ∼220 cycles at a current of 355 mA g−1. Operando Raman spectroscopy during the first lithiation, complemented by ex situ techniques at different cycling stages, demonstrates that both the organic ligands and metal centers actively contribute to Li+ storage. Initially, lithiation occurs primarily at the MOF boundaries, while continuous cycling induces a structural transformation that allows greater accessibility to the inner regions of Fe-HHTP. These results provide a better understanding of the electrochemical and structural behavior of pristine MOFs that allow tailoring their properties for direct application in energy storage devices without the need for high-temperature processes.2025http://zaguan.unizar.es/record/16106610.1039/d5dt00893jhttp://zaguan.unizar.es/record/161066oai:zaguan.unizar.es:161066info:eu-repo/grantAgreement/ES/DGA/E31-23Rinfo:eu-repo/grantAgreement/ES/MCIU/CPP2022-009766info:eu-repo/grantAgreement/ES/MCIU/PID2022-140516OB-I00info:eu-repo/grantAgreement/ES/MICIU/CEX2023-001286-Sinfo:eu-repo/grantAgreement/ES/MICIU/CNS2023-14197Dalton Transactions (2025), [12 pp.]by-nchttps://creativecommons.org/licenses/by-nc/4.0/deed.esinfo:eu-repo/semantics/openAccess