Abstract
Li3VP3O9N was for the first time synthesized from its sodium analogue Na3VP3O9N using a solid–solid Li+/Na+ ion-exchange method. This lithium variant of nitridophosphate is found to possess similar crystal structure (space group P213) as its sodium analogue Na3VP3O9N (a = 9.4507(1) A) but with much smaller lattice parameter (a = 9.1237(1) A). The crystal structure of Li3VP3O9N was solved and refined using combined synchrotron X-ray and time-of-flight neutron powder diffraction data, allowing the three distinct lithium-ion sites to be identified. A lithium bond valence sum difference map calculation suggests the existence of isotropic three-dimensional lithium-ion-conducting pathways with a minimum valence threshold |ΔV| of 0.02. Li3VP3O9N behaves as a promising reversible cathode material for rechargeable lithium-ion batteries with an average V3+/V4+ redox potential of 3.8 V (vs Li+/Li). Both cyclic voltammetry tests and chemical delithiation (using NO2BF4) indicate it is possible to partially remove the ...
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