Oxygen evolution from olivine Mn1–xMxPO4 (M=Fe,Ni,Al,Mg) delithiated cathode materials

Snydacker, David H.; Wolverton, C.

doi:10.1103/physrevb.95.024102

Oxygen evolution from olivine Mn_1–xM_xPO₄ (M=Fe,Ni,Al,Mg) delithiated cathode materials

Journal Article · Tue Jan 03 00:00:00 EST 2017 · Physical Review B

DOI:https://doi.org/10.1103/physrevb.95.024102· OSTI ID:1388301

Snydacker, David H. ^[1]; Wolverton, C. ^[1]

Northwestern Univ., Evanston, IL (United States)

Olivine LiMnPO₄ is a promising cathode material for Li-ion batteries. One drawback of this material is the propensity of its delithiated phase, MnPO₄, to evolve oxygen gas above approximately 200 °C. During thermal runaway of cells, this oxygen gas can burn the electrolyte and other cell components and thereby jeopardize safety. Partial substitution of Mn with M = Fe, Ni, Al, or Mg has been used to improve the lithium intercalation kinetics of Li_xMnPO₄; however, the effect of these substitutions on oxygen evolution is not fully documented. In this paper, we calculate phase diagrams and oxygen evolution diagrams for these Mn_1–xM_xPO₄ delithiated cathode materials. To generate the phase diagrams, we use subregular solid-solution models and fit the energetic parameters of these models to density functional theory calculations of special quasirandom structures. The resulting thermodynamic models describe the effect of mixing on the initial temperature of oxygen evolution and on the cumulative amount of oxygen evolution at elevated temperatures. We find that addition of Fe increases the initial temperature and decreases the cumulative amount of oxygen evolution. Mn_0.5Fe_0.5PO₄ exhibits an initial temperature 50 °C higher than MnPO₄ and releases 70% less oxygen gas at 300 °C. Al is insoluble in MnPO₄, so addition of Al has no affect on the initial temperature. However, Al addition does slightly decrease the amount of oxygen evolution due to an inactive AlPO₄ component. Mg and Ni both decrease the initial temperature of oxygen evolution, and therefore may worsen the safety of MnPO₄.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1388301

Alternate ID(s):: OSTI ID: 1338100

Journal Information:: Physical Review B, Journal Name: Physical Review B Journal Issue: 2 Vol. 95; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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