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This content will become publicly available on March 5, 2017

Title: Li3Mo4P5O24: A two-electron cathode for lithium-ion batteries with three-dimensional diffusion pathways

The structure of the novel compound Li3Mo4P5O24 has been solved from single crystal X-ray diffraction data. The Mo cations in Li3Mo4P5O24 are present in four distinct types of MoO6 octahedra, each of which has one open vertex at the corner participating in a Mo=O double bond and whose other five corners are shared with PO4 tetrahedra. On the basis of a bond valence sum difference map (BVS-DM) analysis, this framework is predicted to support the facile diffusion of Li+ ions, a hypothesis that is confirmed by electrochemical testing data, which show that Li3Mo4P5O24 can be utilized as a rechargeable battery cathode material. It is found that Li can both be removed from and inserted into Li3Mo4P5O24. The involvement of multiple redox processes occurring at the same Mo site is reflected in electrochemical plateaus around 3.8 V associated with the Mo6+/Mo5+ redox couple and 2.2 V associated with the Mo5+/Mo4+ redox couple. The two-electron redox properties of Mo cations in this structure lead to a theoretical capacity of 198 mAh/g. When cycled between 2.0 and 4.3 V versus Li+/Li, an initial capacity of 113 mAh/g is observed with 80% of this capacity retained over the first 20 cycles. Lastly, this compoundmore » therefore represents a rare example of a solid state cathode able to support two-electron redox capacity and provides important general insights about pathways for designing next-generation cathodes with enhanced specific capacities.« less
 [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [3] ;  [1] ;  [1]
  1. State Univ. of New York at Binghamton, Binghamton, NY (United States)
  2. State Univ. of New York at Stony Brook, Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. State Univ. of New York at Stony Brook, Stony Brook, NY (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 0897-4756; R&D Project: CO009; KC0302010
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 7; Journal ID: ISSN 0897-4756
American Chemical Society (ACS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Li-ion batteries; cathodes; molybdenum(5+); phosphates; two-electron transfer