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Title: Li3VP3O9N as a Multielectron Redox Cathode for Li-Ion Battery

Journal Article · · Chemistry of Materials
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
  2. Stony Brook Univ., NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

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) Å) but with much smaller lattice parameter (a = 9.1237(1) Å). 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 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)3N tetrahedral site after removing lithium from this site.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
SC0012704
OSTI ID:
1469792
Report Number(s):
BNL-209033-2018-JAAM
Journal Information:
Chemistry of Materials, Vol. 30, Issue 14; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

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Cited By (3)

Development and Investigation of a NASICON‐Type High‐Voltage Cathode Material for High‐Power Sodium‐Ion Batteries journal December 2019
Development and Investigation of a NASICON‐Type High‐Voltage Cathode Material for High‐Power Sodium‐Ion Batteries journal February 2020
Three-Dimensionally Porous Li-Ion and Li-S Battery Cathodes: A Mini Review for Preparation Methods and Energy-Storage Performance journal March 2019

Linked Research (2)

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