The magnesium insertion capability of Prussian blue (PB) analogue, potassium nickel hexacyanoferrate K0.86Ni[Fe(CN)6]0.954(H2O)0.766 (KNF-086), is demonstrated as a cathode material for rechargeable magnesium-ion batteries using a conventional organic electrolyte. K1.51Ni[Fe(CN)6]0.954(H2O)0.766 is synthesized first, and potassium ions are electrochemically extracted to prepare the KNF-086 cathode. The electrochemical test cell is composed of KNF-086 as the working electrode, an activated carbon as the counter and reference electrode, and 0.5 M Mg(ClO4)2 in acetonitrile as the electrolyte. The cell shows a reversible magnesium insertion/extraction reaction with a discharge capacity of 48.3 mAh g−1 at a 0.2 C rate, and an average discharge voltage at 2.99 V (vs. Mg/Mg2+) that is the highest among the cathode materials ever reported for magnesium-ion batteries. Elemental analysis and Fourier electron-density map analysis from powder X-ray diffraction data confirm that the magnesium-inserted phase is Mg0.27K0.86Ni[Fe(CN)6]0.954(H2O)0.766 (MKNF-086), and the magnesium ions in MKNF-086 are positioned at the center of the large interstitial cavities of cubic PB. Compared to KNF-086, MKNF-086 exhibits a decreased unit cell parameter (0.8%) and volume (2.4%). These results demonstrate that a PB analogue, potassium nickel hexacyanoferrate, could be utilized as a potential cathode material for conventional organic electrolyte-based magnesium-ion batteries.
Bibliographical noteFunding Information:
This research was supported by the Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (2015M3D1A1069707). We also thank the support from LG Chem.
© 2017 Elsevier B.V.
- Crystal structure
- Magnesium-ion battery
- Multivalent-ion battery
- Nonaqueous electrolyte
- Potassium nickel hexacyanoferrate
- Prussian blue analogue