Unveiling the thermodynamic and kinetic properties of NaxFe(SO4)(2) (x=0-2): toward a high-capacity and low-cost cathode material
2016 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 4, no 46, 17960-17969 p.Article in journal (Refereed) Published
The mineral eldfellite, NaFe(SO4)(2), was recently proposed as an inexpensive candidate for the next generation of cathode application in Na-based batteries. Employing the density functional theory framework, we have investigated the phase stability, electrochemical properties and ionic diffusion of this eldfellite cathode material. We showed that the crystal structure undergoes a volume shrinkage of approximate to 8% upon full removal of Na ions with no imaginary frequencies at the Gamma point of phonon dispersion. This evokes the stability of the host structure. According to this result, we proposed structural changes to get higher specific energy by inserting two Na ions per redox-active metal. Our calculations indicate NaV(SO4)(2) as the best candidate with the capability of reversibly inserting two Na ions per redox center and producing an excellent specific energy. The main bottleneck for the application of eldfellite as a cathode is the high activation energies for the Na+ ion hop, which can reach values even higher than 1 eV for the charged state. This effect produces a low ionic insertion rate.
Place, publisher, year, edition, pages
Royal Society of Chemistry, 2016. Vol. 4, no 46, 17960-17969 p.
Activation energy, Crystal structure, Density functional theory, Dispersions, Electrodes, Ions, Metals, Redox reactions, Cath-ode materials, High activation energy, Imaginary frequency, Ionic diffusion, Kinetic properties, Phonon dispersions, Redox-active metals, Volume shrinkage
IdentifiersURN: urn:nbn:se:kth:diva-198916DOI: 10.1039/c6ta05330kISI: 000388505400007ScopusID: 2-s2.0-84999027858OAI: oai:DiVA.org:kth-198916DiVA: diva2:1061413
FunderSwedish Research CouncilSwedish Energy AgencyStandUp
QC 201701022017-01-022016-12-222017-01-02Bibliographically approved