Li-ion batteries have empowered consumer electronics and are now seen as the best choice to propel forward the development of eco-friendly (hybrid) electric vehicles. To enhance the energy density, an intensive search has been made for new polyanionic compounds that have a higher potential for the Fe2+/Fe3+ redox couple. Herein we push this potential to 3.90 V in a new polyanionic material that crystallizes in the triplite structure by substituting as little as 5 atomic per cent of Mn for Fe in Li(Fe1−δMnδ)SO4F. Not only is this the highest voltage reported so far for the Fe2+/Fe3+ redox couple, exceeding that of LiFePO4 by 450 mV, but this new triplite phase is capable of reversibly releasing and reinserting 0.7–0.8 Li ions with a volume change of 0.6% (compared with 7 and 10% for LiFePO4 and LiFeSO4F respectively), to give a capacity of ~125 mA h g−1.
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Many discussions with M. Armand, N. Recham, C. Delacourt, C. Masquelier, D. Larcher, G. Férey, Y. Chabre, C. Frayret and D.W. Murphy are gratefully acknowledged. We thank C. Davoisne for the TEM images and ALISTORE-ERI for sponsoring this research. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The EXAFS measurements were carried out with the support of the Diamond Light Source and we gratefully acknowledge G. Cibin for help with running the X-ray absorption spectroscopy experiments as well as E. J. Schofield and A. V. Chadwick for discussions in analysing the XANES data.
The authors declare no competing financial interests.
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