Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode

doi:10.1021/acs.chemmater.8b03794

Title: Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode

Abstract

Fluorine substitution for oxygen in cation-disordered lithium-excess transition metal oxides (Li_1+xTM_1-xO₂) used as lithium-ion cathodes was recently demonstrated to improve the reversibility of the processes taking place on charge and discharge by reducing the amount of oxygen loss on charge and preventing major structural rearrangements at high voltage. Yet, little is understood about how fluorine incorporates the oxide structure and impacts its electrochemical properties. Here, we use a combination of experimental (solid-state nuclear magnetic resonance (NMR) spectroscopy) and theoretical techniques (density functional theory (DFT) calculations and Monte Carlo simulations) to investigate the evolution of the local structure around fluorine and lithium and the oxidation state of redox-active nickel during charge and discharge of the Li_1.15Ni_0.45Ti_0.3Mo_0.1O_1.85F_0.15 (LNF15) cathode. We show that fluorine doping introduces short-range order in as-synthesized LNF15 by incorporating in lithium-rich sites with five or six lithium nearest neighbors. We observe the emergence of new signals in the ex situ ¹⁹F NMR spectra taken at high states of charge, which we tentatively assign to undercoordinated, diamagnetic fluorine environments seen in our computed models. Our theoretical results also suggest that octahedral nickel ions directly bonded to fluorine follow a different oxidation mechanism than those surrounded by six oxygens, forming Ni³⁺more »« less

Authors:

^[1]; Kitchaev, Daniil ^[2]; Lee, Jinhyuk ^[3]; Ceder, Gerbrand ^[4]

Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Univ. of California, Santa Barbara, CA (United States). Dept. of Materials
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Nuclear Science and Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division

Publication Date:: 2018-09-14

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Robert Bosch LLC, Farmington Hills, MI (United States); Umicore Cobalt & Specialty Materials (CSM), Brussels (Belgium); National Science Foundation (NSF)

OSTI Identifier:: 1473706

Alternate Identifier(s):: OSTI ID: 1571113

Grant/Contract Number:: AC02-05CH11231; DMR 1720256

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Volume: 30; Journal Issue: 19; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Li-ion batteries; Lithium transition metal oxides; NMR; disordered rocksalt cathodes; Monte Carlo simulations; density functional theory

Citation Formats


                    Clément, Raphaële J., Kitchaev, Daniil, Lee, Jinhyuk, and Ceder, Gerbrand. Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.chemmater.8b03794.

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                    Clément, Raphaële J., Kitchaev, Daniil, Lee, Jinhyuk, & Ceder, Gerbrand. Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode.  United States.  doi:10.1021/acs.chemmater.8b03794.

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                    Clément, Raphaële J., Kitchaev, Daniil, Lee, Jinhyuk, and Ceder, Gerbrand. Fri .  
        "Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode".  United States.  doi:10.1021/acs.chemmater.8b03794.  https://www.osti.gov/servlets/purl/1473706.

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@article{osti_1473706,

  title        = {Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode},

  author       = {Clément, Raphaële J. and Kitchaev, Daniil and Lee, Jinhyuk and Ceder, Gerbrand},

  abstractNote = {Fluorine substitution for oxygen in cation-disordered lithium-excess transition metal oxides (Li1+xTM1-xO2) used as lithium-ion cathodes was recently demonstrated to improve the reversibility of the processes taking place on charge and discharge by reducing the amount of oxygen loss on charge and preventing major structural rearrangements at high voltage. Yet, little is understood about how fluorine incorporates the oxide structure and impacts its electrochemical properties. Here, we use a combination of experimental (solid-state nuclear magnetic resonance (NMR) spectroscopy) and theoretical techniques (density functional theory (DFT) calculations and Monte Carlo simulations) to investigate the evolution of the local structure around fluorine and lithium and the oxidation state of redox-active nickel during charge and discharge of the Li1.15Ni0.45Ti0.3Mo0.1O1.85F0.15 (LNF15) cathode. We show that fluorine doping introduces short-range order in as-synthesized LNF15 by incorporating in lithium-rich sites with five or six lithium nearest neighbors. We observe the emergence of new signals in the ex situ 19F NMR spectra taken at high states of charge, which we tentatively assign to undercoordinated, diamagnetic fluorine environments seen in our computed models. Our theoretical results also suggest that octahedral nickel ions directly bonded to fluorine follow a different oxidation mechanism than those surrounded by six oxygens, forming Ni3+ intermediates instead of oxidizing from Ni2+ directly to Ni4+. While the oxidation of Ni2+ toward Ni4+ is incomplete in oxides, due to overlap between the oxygen and the nickel valence states, this result suggests that fluorination may be an efficient strategy to utilize the Ni2+/Ni4+ redox reservoir to a greater extent.},

  doi          = {10.1021/acs.chemmater.8b03794},

  journal      = {Chemistry of Materials},

  number       = 19,

  volume       = 30,

  place        = {United States},

  year         = {2018},

  month        = {9}

}

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DOI: 10.1021/acs.chemmater.8b03794

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Works referencing / citing this record:

Effect of Fluorination on Lithium Transport and Short‐Range Order in Disordered‐Rocksalt‐Type Lithium‐Ion Battery Cathodes
journal, March 2020

Ouyang, Bin; Artrith, Nongnuch; Lun, Zhengyan
Advanced Energy Materials, Vol. 10, Issue 10
DOI: 10.1002/aenm.201903240

Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes
journal, January 2020

Clément, R. J.; Lun, Z.; Ceder, G.
Energy & Environmental Science, Vol. 13, Issue 2
DOI: 10.1039/c9ee02803j

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Abstract

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