Oxygen evolution from olivine Mn1–xMxPO4 (M=Fe,Ni,Al,Mg) delithiated cathode materials
Abstract
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 LixMnPO4; 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 Mn1–xMxPO4 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. Mn0.5Fe0.5PO4 exhibits an initial temperature 50 °C higher than MnPO4 and releases 70% less oxygen gas at 300 °C. Al is insoluble in MnPO4,more »
- Authors:
-
- Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- 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 Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1388301
- Alternate Identifier(s):
- OSTI ID: 1338100
- Grant/Contract Number:
- AC02-06CH11357; AC02-05CH11231; AC02–06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review B
- Additional Journal Information:
- Journal Volume: 95; Journal Issue: 2; Related Information: CEES partners with Argonne National Laboratory (lead); University of Illinois, Urbana-Champaign; Northwest University; Journal ID: ISSN 2469-9950
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; energy storage (including batteries and capacitors); charge transport; materials and chemistry by design; synthesis (novel materials)
Citation Formats
Snydacker, David H., and Wolverton, C. Oxygen evolution from olivine Mn1–xMxPO4 (M=Fe,Ni,Al,Mg) delithiated cathode materials. United States: N. p., 2017.
Web. doi:10.1103/physrevb.95.024102.
Snydacker, David H., & Wolverton, C. Oxygen evolution from olivine Mn1–xMxPO4 (M=Fe,Ni,Al,Mg) delithiated cathode materials. United States. https://doi.org/10.1103/physrevb.95.024102
Snydacker, David H., and Wolverton, C. Tue .
"Oxygen evolution from olivine Mn1–xMxPO4 (M=Fe,Ni,Al,Mg) delithiated cathode materials". United States. https://doi.org/10.1103/physrevb.95.024102. https://www.osti.gov/servlets/purl/1388301.
@article{osti_1388301,
title = {Oxygen evolution from olivine Mn1–xMxPO4 (M=Fe,Ni,Al,Mg) delithiated cathode materials},
author = {Snydacker, David H. and Wolverton, C.},
abstractNote = {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 LixMnPO4; 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 Mn1–xMxPO4 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. Mn0.5Fe0.5PO4 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.},
doi = {10.1103/physrevb.95.024102},
journal = {Physical Review B},
number = 2,
volume = 95,
place = {United States},
year = {Tue Jan 03 00:00:00 EST 2017},
month = {Tue Jan 03 00:00:00 EST 2017}
}
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