Structure and Lithium Ion Dynamics in Fluoride Doped Cubic LLZO Garnet for Li Solid State Battery Applications

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Structure and Lithium Ion Dynamics in Fluoride Doped Cubic LLZO Garnet for Li Solid State Battery Applications. / yeandel, s; chapman, B; Slater, Peter; goddard, P .

In: Journal of Physical Chemistry C, 10.11.2018.

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@article{5d4f1bdd7d6b458db526c484c276d569,
title = "Structure and Lithium Ion Dynamics in Fluoride Doped Cubic LLZO Garnet for Li Solid State Battery Applications",
abstract = "The lithium-stuffed garnet LLZO (Li7La3Zr2O12), when suitably doped, is a promising candidate material for use as a solid state electrolyte within advanced Li-ion batteries. It possesses the thermal and mechanical stability of many inorganic ceramics, while exhibiting the high Li+ ionic conductivities often associated with conventional liquid electrolytes, making it an ideal component for large scale energy storage. However, only the high temperature cubic phase has any meaningful Li-ion conductivity. Typically the formation of this phase is achieved through cation doping (e.g. Al3+ on the Li site) to lower the Li content and so disrupt Li ordering. However, Li site doping, in particular, may potentially lead to some disruption of the Li ion conduction pathways and sub-optimal ionic conductivities. Consequently, other novel doping strategies involving the anion site is gaining traction, such as F- for O2- as an alternative strategy to lower the Li content without directly blocking the lithium diffusion pathways. Classical potentials-based simulations have been employed to simulate the incorporation of fluoride anions into LLZO. Low incorporation energies have been calculated suggesting fluoride anions are stable on the oxygen sites with a compensating lithium ion vacancy defect. Molecular dynamics (MD) calculations suggest a definitive phase transition to the more desirable cubic phase of LLZO when doped with fluoride at temperatures significantly lower than the tetragonal-cubic phase transition found for pure LLZO. Concurrently, the lithium ion transport properties are shown to improve in the fluoride doped samples particularly at low temperatures due to the stabilisation of the cubic phase, suggesting anion doping of garnet systems may be a compelling alternative route to optimise the ionic conductivity.",
author = "s yeandel and B chapman and Peter Slater and P goddard",
year = "2018",
month = nov,
day = "10",
doi = "10.1021/acs.jpcc.8b07704",
language = "English",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",

}

RIS

TY - JOUR

T1 - Structure and Lithium Ion Dynamics in Fluoride Doped Cubic LLZO Garnet for Li Solid State Battery Applications

AU - yeandel, s

AU - chapman, B

AU - Slater, Peter

AU - goddard, P

PY - 2018/11/10

Y1 - 2018/11/10

N2 - The lithium-stuffed garnet LLZO (Li7La3Zr2O12), when suitably doped, is a promising candidate material for use as a solid state electrolyte within advanced Li-ion batteries. It possesses the thermal and mechanical stability of many inorganic ceramics, while exhibiting the high Li+ ionic conductivities often associated with conventional liquid electrolytes, making it an ideal component for large scale energy storage. However, only the high temperature cubic phase has any meaningful Li-ion conductivity. Typically the formation of this phase is achieved through cation doping (e.g. Al3+ on the Li site) to lower the Li content and so disrupt Li ordering. However, Li site doping, in particular, may potentially lead to some disruption of the Li ion conduction pathways and sub-optimal ionic conductivities. Consequently, other novel doping strategies involving the anion site is gaining traction, such as F- for O2- as an alternative strategy to lower the Li content without directly blocking the lithium diffusion pathways. Classical potentials-based simulations have been employed to simulate the incorporation of fluoride anions into LLZO. Low incorporation energies have been calculated suggesting fluoride anions are stable on the oxygen sites with a compensating lithium ion vacancy defect. Molecular dynamics (MD) calculations suggest a definitive phase transition to the more desirable cubic phase of LLZO when doped with fluoride at temperatures significantly lower than the tetragonal-cubic phase transition found for pure LLZO. Concurrently, the lithium ion transport properties are shown to improve in the fluoride doped samples particularly at low temperatures due to the stabilisation of the cubic phase, suggesting anion doping of garnet systems may be a compelling alternative route to optimise the ionic conductivity.

AB - The lithium-stuffed garnet LLZO (Li7La3Zr2O12), when suitably doped, is a promising candidate material for use as a solid state electrolyte within advanced Li-ion batteries. It possesses the thermal and mechanical stability of many inorganic ceramics, while exhibiting the high Li+ ionic conductivities often associated with conventional liquid electrolytes, making it an ideal component for large scale energy storage. However, only the high temperature cubic phase has any meaningful Li-ion conductivity. Typically the formation of this phase is achieved through cation doping (e.g. Al3+ on the Li site) to lower the Li content and so disrupt Li ordering. However, Li site doping, in particular, may potentially lead to some disruption of the Li ion conduction pathways and sub-optimal ionic conductivities. Consequently, other novel doping strategies involving the anion site is gaining traction, such as F- for O2- as an alternative strategy to lower the Li content without directly blocking the lithium diffusion pathways. Classical potentials-based simulations have been employed to simulate the incorporation of fluoride anions into LLZO. Low incorporation energies have been calculated suggesting fluoride anions are stable on the oxygen sites with a compensating lithium ion vacancy defect. Molecular dynamics (MD) calculations suggest a definitive phase transition to the more desirable cubic phase of LLZO when doped with fluoride at temperatures significantly lower than the tetragonal-cubic phase transition found for pure LLZO. Concurrently, the lithium ion transport properties are shown to improve in the fluoride doped samples particularly at low temperatures due to the stabilisation of the cubic phase, suggesting anion doping of garnet systems may be a compelling alternative route to optimise the ionic conductivity.

U2 - 10.1021/acs.jpcc.8b07704

DO - 10.1021/acs.jpcc.8b07704

M3 - Article

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

ER -