Comprehensive multi-technique study of the electrochemical lithiation of Fe ₃ O ₄ with different particle sizes under operando conditions
10 affiliations
- 1Materials Science and Engineering
- 2Uppsala University
- 3Faculty of Chemistry
- 4University of Duisburg-Essen
- 5ALBA Synchrotron Light Source
- 6Deutsches Elektronen-Synchrotron (DESY)
- 7European Spallation Source
- 8Jülich Centre for Neutron Science (JCNS-1)
- 9Chemistry-Ångström
- 10MAX IV Laboratory
Abstract
Fe3O4 is a conversion-type anode material with high storage capacity that suffers from limited cycling performance. Nanosizing Fe3O4 is one promising strategy to enhance its cycling stability and overall electrochemical performance; however, the details of particle size dependent reaction kinetics remain poorly understood. We investigate the conversion reactions of bulk- and 50 nm-sized cubic Fe3O4 particles as active material using a multi-technique approach, by combining operando XRD, SAXS and magnetometry techniques. The results from the operando XRD and SAXS indicate that during initial lithiation reaction, the bulk electrode undergoes phase reduction with amorphization and formation of metallic iron nanograins, whereas the nanoparticle Fe3O4 retains its ccp oxygen anion framework throughout the lithiation process, hindering structural breakdown and amorphization and delaying the the growth of metallic iron nano grains. Operando vibrating sample magnetometry isused to cross-check the transformation and presence of metallic iron nanodomains owing to its unique sensitivity to local structural details hidden in conventional XRD. The reaction products were found to differ when time-resolved investigations are compared to ex-situ prepared specimens. These results highlight the critical importance of integrating complementary operando techniques to ex situ methods, to capture particle size–dependent lithiation pathways and relaxation mechanisms in conversion-type electrodes.
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BibTeX
@misc{ulusoy2026comprehensive,
title = {{Comprehensive multi-technique study of the electrochemical lithiation of Fe ₃ O ₄ with different particle sizes under operando conditions}},
author = {Seda Ulusoy* and Hyeyun Kim and Leonhard Rochels and Martin Kapuscinski and Tereza Václav̊u and Ilaria Lucentini and Xiao Sun and Mikhail Feygenson and Mario Valvo and Tomás S. Plivelic and Sabrina Disch and Peter Svedlindh and German Salazar Alvarez},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010343/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010343/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Comprehensive multi-technique study of the electrochemical lithiation of Fe ₃ O ₄ with different particle sizes under operando conditions
AU - Seda Ulusoy*
AU - Hyeyun Kim
AU - Leonhard Rochels
AU - Martin Kapuscinski
AU - Tereza Václav̊u
AU - Ilaria Lucentini
AU - Xiao Sun
AU - Mikhail Feygenson
AU - Mario Valvo
AU - Tomás S. Plivelic
AU - Sabrina Disch
AU - Peter Svedlindh
AU - German Salazar Alvarez
PY - 2026
DA - 2026/10/13
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010343/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010343/v1
AB - Fe3O4 is a conversion-type anode material with high storage capacity that suffers from limited cycling performance. Nanosizing Fe3O4 is one promising strategy to enhance its cycling stability and overall electrochemical performance; however, the details of particle size dependent reaction kinetics remain poorly understood. We investigate the conversion reactions of bulk- and 50 nm-sized cubic Fe3O4 particles as active material using a multi-technique approach, by combining operando XRD, SAXS and magnetometry techniques. The results from the operando XRD and SAXS indicate that during initial lithiation reaction, the bulk electrode undergoes phase reduction with amorphization and formation of metallic iron nanograins, whereas the nanoparticle Fe3O4 retains its ccp oxygen anion framework throughout the lithiation process, hindering structural breakdown and amorphization and delaying the the growth of metallic iron nano grains. Operando vibrating sample magnetometry isused to cross-check the transformation and presence of metallic iron nanodomains owing to its unique sensitivity to local structural details hidden in conventional XRD. The reaction products were found to differ when time-resolved investigations are compared to ex-situ prepared specimens. These results highlight the critical importance of integrating complementary operando techniques to ex situ methods, to capture particle size–dependent lithiation pathways and relaxation mechanisms in conversion-type electrodes.
ER -