Exploring a new synthesis route to lithium-excess disordered rock salt (DRX) cathode materials

Matthew S. Chambers; Tianyu Li; Zhilin Liang; Jong Keum; Kevin H. Stone; Raphaële J. Clément; Beth L. Armstrong; Ethan C. Self

doi:10.1039/d4ma01287a

Exploring a new synthesis route to lithium-excess disordered rock salt (DRX) cathode materials

Matthew S. Chambers
, Tianyu Li
, Zhilin Liang
, Jong Keum
, Kevin H. Stone
, Raphaële J. Clément
, Beth L. Armstrong
, Ethan C. Self

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

Lithium-excess disordered rock salt (DRX) materials are promising candidates for Co/Ni-free Li-ion cathodes due to their high specific energy (800+ W h kg⁻¹) and compositional flexibility. DRX cathodes are typically synthesized using solid-state reactions, which are difficult to scale and provide little-to-no control over particle morphology. To address this bottleneck, the present study reports a two-step, solution-based reaction route to prepare Mn/Ti-based DRX oxyfluoride cathodes with nominal compositions of Li_1.25Mn_0.5Ti_0.3O_1.95F_0.05 and Li_1.35Mn_0.7Ti_0.1O_1.85F_0.15. More specifically, a glycine-nitrate combustion reaction is used to produce a lithiated transition metal oxide, which is further reacted with LiF to produce high-purity DRX powders. Remarkably, this route yields 80-90% pure DRX after annealing for 1 h at 800-1000 °C, and ¹⁹F solid-state nuclear magnetic resonance (ssNMR) spectra demonstrate that F⁻ anions are successfully incorporated into the DRX structure. Cathodes prepared using this approach exhibit promising electrochemical performance, with Li_1.35Mn_0.7Ti_0.1O_1.85F_0.15 attaining reversible capacities ∼210 mA h g⁻¹ and moderate cycling stability in half cells (65% capacity retention over 150 cycles). Overall, these results demonstrate that utilizing novel metal oxide precursors presents a viable and largely unexplored method to produce high-performance Co/Ni-free DRX cathodes.

Original language	English
Pages (from-to)	2990-3001
Number of pages	12
Journal	Materials Advances
Volume	6
Issue number	9
DOIs	https://doi.org/10.1039/d4ma01287a
State	Published - Apr 23 2025

Funding

The authors would like to thank Khryslyn Araño and Ji-young Ock of the Oak Ridge National Laboratory for providing advice with casting electrodes and aiding with coin cell assembly, respectively. The authors would also like to thank Gabriel Veith of the Oak Ridge National Laboratory for providing mentorship and supervision to Matthew S. Chambers. SEM imaging and some XRD measurements were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. Research conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the US Department of Energy (DOE) was sponsored by the Vehicle Technologies Office (VTO) under the Office of Energy Efficiency and Renewable Energy (EERE). Research conducted at UC Santa Barbara was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office under the Applied Battery Materials Program of the US Department of Energy (DOE) under contract number DE-AC02-05CH11231 (DRX+). This work made use of the MRL MRSEC Spectroscopy Facility at UC Santa Barbara (DMR-2308708), a member of the Materials Research Facilities Network (https://www.mrfn.org). Notice: This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://www.energy.gov/doe-public-access-plan). The authors would like to thank Khryslyn Araño and Ji-young Ock of the Oak Ridge National Laboratory for providing advice with casting electrodes and aiding with coin cell assembly, respectively. The authors would also like to thank Gabriel Veith of the Oak Ridge National Laboratory for providing mentorship and supervision to Matthew S. Chambers. SEM imaging and some XRD measurements were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. Research conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the US Department of Energy (DOE) was sponsored by the Vehicle Technologies Office (VTO) under the Office of Energy Efficiency and Renewable Energy (EERE). Research conducted at UC Santa Barbara was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office under the Applied Battery Materials Program of the US Department of Energy (DOE) under contract number DE-AC02-05CH11231 (DRX+). This work made use of the MRL MRSEC Spectroscopy Facility at UC Santa Barbara (DMR–2308708), a member of the Materials Research Facilities Network ( https://www.mrfn.org ). Notice: This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( https://www.energy.gov/doe-public-access-plan ).

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10.1039/d4ma01287a

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title = "Exploring a new synthesis route to lithium-excess disordered rock salt (DRX) cathode materials",

abstract = "Lithium-excess disordered rock salt (DRX) materials are promising candidates for Co/Ni-free Li-ion cathodes due to their high specific energy (800+ W h kg−1) and compositional flexibility. DRX cathodes are typically synthesized using solid-state reactions, which are difficult to scale and provide little-to-no control over particle morphology. To address this bottleneck, the present study reports a two-step, solution-based reaction route to prepare Mn/Ti-based DRX oxyfluoride cathodes with nominal compositions of Li1.25Mn0.5Ti0.3O1.95F0.05 and Li1.35Mn0.7Ti0.1O1.85F0.15. More specifically, a glycine-nitrate combustion reaction is used to produce a lithiated transition metal oxide, which is further reacted with LiF to produce high-purity DRX powders. Remarkably, this route yields 80-90\% pure DRX after annealing for 1 h at 800-1000 °C, and 19F solid-state nuclear magnetic resonance (ssNMR) spectra demonstrate that F− anions are successfully incorporated into the DRX structure. Cathodes prepared using this approach exhibit promising electrochemical performance, with Li1.35Mn0.7Ti0.1O1.85F0.15 attaining reversible capacities ∼210 mA h g−1 and moderate cycling stability in half cells (65\% capacity retention over 150 cycles). Overall, these results demonstrate that utilizing novel metal oxide precursors presents a viable and largely unexplored method to produce high-performance Co/Ni-free DRX cathodes.",

author = "Chambers, \{Matthew S.\} and Tianyu Li and Zhilin Liang and Jong Keum and Stone, \{Kevin H.\} and Cl{\'e}ment, \{Rapha{\"e}le J.\} and Armstrong, \{Beth L.\} and Self, \{Ethan C.\}",

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doi = "10.1039/d4ma01287a",

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AU - Chambers, Matthew S.

AU - Li, Tianyu

AU - Liang, Zhilin

AU - Keum, Jong

AU - Stone, Kevin H.

AU - Clément, Raphaële J.

AU - Armstrong, Beth L.

AU - Self, Ethan C.

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Y1 - 2025/4/23

N2 - Lithium-excess disordered rock salt (DRX) materials are promising candidates for Co/Ni-free Li-ion cathodes due to their high specific energy (800+ W h kg−1) and compositional flexibility. DRX cathodes are typically synthesized using solid-state reactions, which are difficult to scale and provide little-to-no control over particle morphology. To address this bottleneck, the present study reports a two-step, solution-based reaction route to prepare Mn/Ti-based DRX oxyfluoride cathodes with nominal compositions of Li1.25Mn0.5Ti0.3O1.95F0.05 and Li1.35Mn0.7Ti0.1O1.85F0.15. More specifically, a glycine-nitrate combustion reaction is used to produce a lithiated transition metal oxide, which is further reacted with LiF to produce high-purity DRX powders. Remarkably, this route yields 80-90% pure DRX after annealing for 1 h at 800-1000 °C, and 19F solid-state nuclear magnetic resonance (ssNMR) spectra demonstrate that F− anions are successfully incorporated into the DRX structure. Cathodes prepared using this approach exhibit promising electrochemical performance, with Li1.35Mn0.7Ti0.1O1.85F0.15 attaining reversible capacities ∼210 mA h g−1 and moderate cycling stability in half cells (65% capacity retention over 150 cycles). Overall, these results demonstrate that utilizing novel metal oxide precursors presents a viable and largely unexplored method to produce high-performance Co/Ni-free DRX cathodes.

AB - Lithium-excess disordered rock salt (DRX) materials are promising candidates for Co/Ni-free Li-ion cathodes due to their high specific energy (800+ W h kg−1) and compositional flexibility. DRX cathodes are typically synthesized using solid-state reactions, which are difficult to scale and provide little-to-no control over particle morphology. To address this bottleneck, the present study reports a two-step, solution-based reaction route to prepare Mn/Ti-based DRX oxyfluoride cathodes with nominal compositions of Li1.25Mn0.5Ti0.3O1.95F0.05 and Li1.35Mn0.7Ti0.1O1.85F0.15. More specifically, a glycine-nitrate combustion reaction is used to produce a lithiated transition metal oxide, which is further reacted with LiF to produce high-purity DRX powders. Remarkably, this route yields 80-90% pure DRX after annealing for 1 h at 800-1000 °C, and 19F solid-state nuclear magnetic resonance (ssNMR) spectra demonstrate that F− anions are successfully incorporated into the DRX structure. Cathodes prepared using this approach exhibit promising electrochemical performance, with Li1.35Mn0.7Ti0.1O1.85F0.15 attaining reversible capacities ∼210 mA h g−1 and moderate cycling stability in half cells (65% capacity retention over 150 cycles). Overall, these results demonstrate that utilizing novel metal oxide precursors presents a viable and largely unexplored method to produce high-performance Co/Ni-free DRX cathodes.

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DO - 10.1039/d4ma01287a

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JO - Materials Advances

JF - Materials Advances

IS - 9

ER -

Exploring a new synthesis route to lithium-excess disordered rock salt (DRX) cathode materials

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