TY - JOUR
T1 - Na-Ion storage in iron hydroxide phosphate hydrate through a reversible crystalline-to-amorphous phase transition
AU - Henriksen, Christian
AU - Karlsen, Martin Aaskov
AU - Jakobsen, Christian Lund
AU - Ravnsbæk, Dorthe Bomholdt
PY - 2020
Y1 - 2020
N2 - Iron(iii) hydroxide phosphate hydrate Fe1.13(PO4)(OH)0.39(H2O)0.61 is investigated for the first time as a Na-ion battery cathode, which reveals that the material exhibits similar storage capacities for Na-and Li-ions at relatively low current rates (i.e. C/10). Interestingly, operando X-ray diffraction shows that insertion of Na-ions induces a solid solution transition in the crystalline Fe1.13(PO4)(OH)0.39(H2O)0.61 end-member simultaneously with a major amorphization. This result adds to the series of observations of phosphate-based materials undergoing order-disorder transitions during Na-ion storage. Fe1.13(PO4)(OH)0.39(H2O)0.61 is thus ideal for enhancing our knowledge on such phenomena. To this end, using total X-ray scattering with pair distribution function analysis, we show that the amorphous phase is Na-rich NaxFe1.13(PO4)(OH)0.39(H2O)0.61 with the local [FeO6]-[PO4] motif retained but with coherence lengths of only ca. 0.6 nm. Our investigation also reveals that the crystallinity of Fe1.13(PO4)(OH)0.39(H2O)0.61 is regained upon Na-extraction (battery recharge), i.e. the order-disorder transition is reversible.
AB - Iron(iii) hydroxide phosphate hydrate Fe1.13(PO4)(OH)0.39(H2O)0.61 is investigated for the first time as a Na-ion battery cathode, which reveals that the material exhibits similar storage capacities for Na-and Li-ions at relatively low current rates (i.e. C/10). Interestingly, operando X-ray diffraction shows that insertion of Na-ions induces a solid solution transition in the crystalline Fe1.13(PO4)(OH)0.39(H2O)0.61 end-member simultaneously with a major amorphization. This result adds to the series of observations of phosphate-based materials undergoing order-disorder transitions during Na-ion storage. Fe1.13(PO4)(OH)0.39(H2O)0.61 is thus ideal for enhancing our knowledge on such phenomena. To this end, using total X-ray scattering with pair distribution function analysis, we show that the amorphous phase is Na-rich NaxFe1.13(PO4)(OH)0.39(H2O)0.61 with the local [FeO6]-[PO4] motif retained but with coherence lengths of only ca. 0.6 nm. Our investigation also reveals that the crystallinity of Fe1.13(PO4)(OH)0.39(H2O)0.61 is regained upon Na-extraction (battery recharge), i.e. the order-disorder transition is reversible.
U2 - 10.1039/d0nr01922d
DO - 10.1039/d0nr01922d
M3 - Journal article
C2 - 32515762
AN - SCOPUS:85087110877
VL - 12
SP - 12824
EP - 12830
JO - Nanoscale
JF - Nanoscale
SN - 2040-3364
IS - 24
ER -