Solid-state vs. spray-drying synthesis for Mg-doped P2–Na₀.₆₇Fe₀.₅Mn₀.₅O₂ as a cathode material for sodium-ion batteries

Title data

Canini, Mattia ; Callegari, Daniele ; Bianchini, Matteo ; Quartarone, Eliana:
Solid-state vs. spray-drying synthesis for Mg-doped P2–Na₀.₆₇Fe₀.₅Mn₀.₅O₂ as a cathode material for sodium-ion batteries.
In: Journal of Materials Chemistry A. (2025) .
ISSN 2050-7496
DOI: https://doi.org/10.1039/D5TA04988A

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Abstract in another language

Combining spray-drying synthesis with Mg(ii) doping offers a promising route to prepare high-performance P2-layered cathodes for sodium-ion batteries. Among the different cathodes studied for Sodium-Ion Batteries (SIBs), the P2-layered oxide structure has garnered significant attention due to its electrochemical properties. However, several critical issues must still be addressed to enable large-scale commercialization, including the numerous phase transitions that the structure undergoes during cycling at high potentials (4 V) and the low Na content in the pristine material. In this work, starting from the promising and sustainable Na 0.67 Mn 0.5 Fe 0.5 O 2 , we developed new cathodes by partially replacing Fe with Mg. In addition to studying the role of Mg( ii ), a cation known for its stabilizing properties, we also evaluated the influence of two different synthesis methods on the structural and functional properties. In particular, spray-drying proved to be very promising compared to the conventional solid-state synthesis, as it leads to materials with morphology and microstructures more compatible with application as cathodes for batteries. The calculated Na diffusion coefficient ( D Na + ) is more than two orders of magnitude higher for P2–Na 0.67 Mn 0.5 Fe 0.3 Mg 0.2 O 2 prepared by spray-drying than that by the solid-state synthesis (10 −8 vs. 10 −10 cm 2 s −1 ). In line with this result, the capacity retention after 100 cycles @ 1C is also significantly higher (72% vs. 81%). Compared with P2–Na 0.67 Mn 0.5 Fe 0.5 O 2 , Mg( ii )-doping significantly improves the cathodic performances of the spray-dried materials, increasing capacity retention after 200 cycles at 1C from 39% to 69%. In conclusion, we confirmed that the choice of the correct synthesis route, combined with optimization of elemental composition, plays a crucial role in the development of high performance materials for SIBs.

Further data

Item Type:	Article in a journal
Refereed:	Yes
Institutions of the University:	Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Lehrstuhl Anorganische Aktivmaterialien für elektrochemische Energiespeicher > Lehrstuhl Anorganische Aktivmaterialien für elektrochemische Energiespeicher - Univ.-Prof. Dr. Matteo Bianchini Research Institutions > Central research institutes > Bayerisches Zentrum für Batterietechnik - BayBatt
Result of work at the UBT:	Yes
DDC Subjects:	500 Science > 540 Chemistry
Date Deposited:	28 Aug 2025 06:08
Last Modified:	28 Aug 2025 06:08
URI:	https://eref.uni-bayreuth.de/id/eprint/94551