Journal
CHEMISTRY OF MATERIALS
Volume 30, Issue 14, Pages 4609-4616Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.8b01114
Keywords
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Funding
- U.S. Department of Energy, Office of Basic Energy Sciences [DE-SC0012583, DE-SC0012704]
- Office of Vehicle Technologies of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program [DE-SC0012704]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0012704]
- Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy
- U.S. Department of Energy (DOE) [DE-SC0012583] Funding Source: U.S. Department of Energy (DOE)
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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 P2(1)3) as its sodium analogue Na3VP3O9N (a = 9.4507(1) angstrom) but with much smaller lattice parameter (a = 9.1237(1) angstrom). 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 vertical bar Delta V vertical bar 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 second lithium from the structure, though only at very high potentials (>4.9 V vs Li+/Li). It is also found that the unit cell volume of this compound expands instead of shrinking upon lithium removal, a rare phenomenon for polyanion-based cathodes. This abnormal volume expansion is found to be associated with the drastic expansion of the Li1(O1)N-3 tetrahedral site after removing lithium from this site.
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