Understanding the limits to short-range order suppression in many-component disordered rock salt lithium-ion cathode materials

Squires, Alexander G.; Scanlon, David O.

doi:10.1039/d3ta02088f

Cited by 7 publications

(3 citation statements)

References 74 publications

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“…8–12 Several transition metals such as Mn, Ti, V, and Cr have been utilized to synthesize DRXs with capacities of up to 300 mA h g −1 . 13–17 Transition metal cation mixing, 11,18 short-range ordered structure analysis, 19–22 and the Li + migration mechanism 23–26 are highly researched to activate the high capacity and improve the rate performance of DRXs. Recently, Konuma et al reported a “near dimensionally invariable” material Li 8/7 Ti 2/7 V 4/7 O 2 , which was encapsulated in Li 6 PS 5 Cl-based ASSBs using a PEEK mold and achieved a capacity of 300 mA h g −1 at a high operating pressure of 200 MPa and a current of 0.2 C (60 mA g −1 ).…”

Section: Introductionmentioning

confidence: 99%

Lithium-rich sulfide Li₂Ti_1−xSi_xS₃ cathode materials optimized through Si-doping for high-capacity all-solid-state lithium-ion batteries

Hu,

Zhang,

Liu

et al. 2024

J. Mater. Chem. A

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Section: Introductionmentioning

confidence: 99%

Lithium-rich sulfide Li₂Ti_1−xSi_xS₃ cathode materials optimized through Si-doping for high-capacity all-solid-state lithium-ion batteries

Hu,

Zhang,

Liu

et al. 2024

J. Mater. Chem. A

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“…Heteroanionic materials, which contain two or more anionic species, offer compositional and structural flexibility not found in otherwise analogous homoanionic materials. − As such, controlling the relative stoichiometries and crystallographic arrangements of the anion species in heteroanionic materials allows their properties to be tuned. , This compositional and structural versatility means that heteroanionic materials find applications across a range of critical technologies, including thermoelectrics, photocatalysis, , and energy storage. − …”

Section: Introductionmentioning

confidence: 99%

Correlated Anion Disorder in Heteroanionic Cubic TiOF₂

Legein,

Morgan,

Squires

et al. 2024

J. Am. Chem. Soc.

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Resolving anion configurations in heteroanionic materials is crucial for understanding and controlling their properties. For anion-disordered oxyfluorides, conventional Bragg diffraction cannot fully resolve the anionic structure, necessitating alternative structure determination methods. We have investigated the anionic structure of anion-disordered cubic (ReO 3 -type) TiOF 2 using X-ray pair distribution function (PDF), 19 F MAS NMR analysis, density functional theory (DFT), cluster expansion modeling, and genetic-algorithm structure prediction. Our computational data predict short-range anion ordering in TiOF 2 , characterized by predominant cis-[O 2 F 4 ] titanium coordination, resulting in correlated anion disorder at longer ranges. To validate our predictions, we generated partially disordered supercells using genetic-algorithm structure prediction and computed simulated Xray PDF data and 19 F MAS NMR spectra, which we compared directly to experimental data. To construct our simulated 19 F NMR spectra, we derived new transformation functions for mapping calculated magnetic shieldings to predicted magnetic chemical shifts in titanium (oxy)fluorides, obtained by fitting DFT-calculated magnetic shieldings to previously published experimental chemical shift data for TiF 4 . We find good agreement between our simulated and experimental data, which supports our computationally predicted structural model and demonstrates the effectiveness of complementary experimental and computational techniques in resolving anionic structure in anion-disordered oxyfluorides. From additional DFT calculations, we predict that increasing anion disorder makes lithium intercalation more favorable by, on average, up to 2 eV, highlighting the significant effect of variations in short-range order on the intercalation properties of anion-disordered materials.

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“…This could be inspired by the efficient methods for selecting training data for conventional cluster expansions − and should be highly relevant for more complex compositions. For these, conventional cluster expansion modeling is already faced with challenges due to the many compositional degrees of freedom, − and we expect this methodology to face similar challenges. Furthermore, improvements may be observed with other types of machine learning architecture such as equivariant neural network potentials. , …”

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confidence: 99%

Low-Cost Vibrational Free Energies in Solid Solutions with Machine Learning Force Fields

Tolborg,

Walsh

2023

J. Phys. Chem. Lett.

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The rational design of alloys and solid solutions relies on accurate computational predictions of phase diagrams. The cluster expansion method has proven to be a valuable tool for studying disordered crystals. However, the effects of vibrational entropy are commonly neglected due to the computational cost. Here, we devise a method for including the vibrational free energy in cluster expansions with a low computational cost by fitting a machine learning force field (MLFF) to the relaxation trajectories available from cluster expansion construction. We demonstrate our method for two (pseudo)binary systems, Na 1– x K x Cl and Ag 1– x Pd x , for which accurate phonon dispersions and vibrational free energies are derived from the MLFF. For both systems, the inclusion of vibrational effects results in significantly better agreement with miscibility gaps in experimental phase diagrams. This methodology can allow routine inclusion of vibrational effects in calculated phase diagrams and thus more accurate predictions of properties and stability for mixtures of materials.

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Understanding the limits to short-range order suppression in many-component disordered rock salt lithium-ion cathode materials

Abstract: Suppressing unfavourable short-range ordering in disordered rock salt lithium-ion cathode materials is seen as a key research goal on their route to commercialisation. In this study we use cluster-expansion-driven Monte...

Cited by 7 publications

References 74 publications

Lithium-rich sulfide Li₂Ti_1−xSi_xS₃ cathode materials optimized through Si-doping for high-capacity all-solid-state lithium-ion batteries

Lithium-rich sulfide Li₂Ti_1−xSi_xS₃ cathode materials optimized through Si-doping for high-capacity all-solid-state lithium-ion batteries

Correlated Anion Disorder in Heteroanionic Cubic TiOF₂

Low-Cost Vibrational Free Energies in Solid Solutions with Machine Learning Force Fields

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Understanding the limits to short-range order suppression in many-component disordered rock salt lithium-ion cathode materials

Abstract: Suppressing unfavourable short-range ordering in disordered rock salt lithium-ion cathode materials is seen as a key research goal on their route to commercialisation. In this study we use cluster-expansion-driven Monte...

Cited by 7 publications

References 74 publications

Lithium-rich sulfide Li2Ti1−xSixS3 cathode materials optimized through Si-doping for high-capacity all-solid-state lithium-ion batteries

Lithium-rich sulfide Li2Ti1−xSixS3 cathode materials optimized through Si-doping for high-capacity all-solid-state lithium-ion batteries

Correlated Anion Disorder in Heteroanionic Cubic TiOF2

Low-Cost Vibrational Free Energies in Solid Solutions with Machine Learning Force Fields

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Product

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Lithium-rich sulfide Li₂Ti_1−xSi_xS₃ cathode materials optimized through Si-doping for high-capacity all-solid-state lithium-ion batteries

Lithium-rich sulfide Li₂Ti_1−xSi_xS₃ cathode materials optimized through Si-doping for high-capacity all-solid-state lithium-ion batteries

Correlated Anion Disorder in Heteroanionic Cubic TiOF₂