Going against the Grain: Atomistic Modeling of Grain Boundaries in Solid Electrolytes for Solid-State Batteries

Dawson, James A.

doi:10.1021/acsmaterialsau.3c00064

Cited by 4 publications

(1 citation statement)

References 86 publications

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“…This may make an important contribution to the low ionic conductivity in the SCL. Besides this defect-deficient region in the SCL, the GB cores also have a detrimental impact on ion transport, which is another potential origin of the low ionic conductivity of the SCL. − …”

Section: Design Of Inorganic Solid Electrolytes With Enhanced Ionic C...mentioning

confidence: 99%

Computational Design of Inorganic Solid-State Electrolyte Materials for Lithium-Ion Batteries

Ma,

2024

Acc. Mater. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: Solid-state electrolytes hold great promise for advancing electrochemical energy storage devices. Advanced batteries based on solid electrolytes, particularly all-solid-state lithiummetal batteries, hold the potential to simultaneously address both high energy density and safety concerns associated with traditional lithium-ion batteries. Ideally, solid electrolytes should exhibit a high ionic conductivity at room temperature. In practical applications, other properties, such as electrochemical stability and compatibility with electrodes, are equally important. However, the pursuit of a single solid electrolyte possessing all of these properties remains challenging. Simulation techniques play an important role in the design of solid electrolyte materials, bypassing the difficulty of chemical synthesis and structural characterization. In these simulations, ionic conduction within bulk electrolytes and the ion deposition and stripping processes at the charged electrode−electrolyte interface can be investigated. By providing the flexibility to construct electrolyte models and explore structural evolution at multiple scales, simulation techniques facilitate the rational design of advanced solid electrolytes that maximizes their advantages and mitigates limitations. This account is initiated by introducing fundamental theories and simulation techniques to investigate the ionic conductivity of an inorganic solid electrolyte. Subsequently, we present our recent progress in designing high ionic conductivity electrolytes by increasing the concentration of Li vacancies, by tuning the type of defects, by constructing diffusion pathways, and by avoiding ion crowding. At last, the electrochemical stability of inorganic solid electrolytes and their compatibility with lithium-metal electrodes are addressed.In bulk electrolytes, increasing the defect concentration can often enhance the ionic conductivity. For instance, to surpass the upper limit of Li vacancy concentration without compromising structural stability, we adopt an antispinel crystal structure, enhancing Li mobility within the Li 3 OBr electrolyte. The type of defects also matters. Instead of O doping, we propose to introduce Li interstitials effectively through S doping, significantly reducing lattice distortion and eliminating the anchoring effect of Li around the O dopant.Compared to the electrolyte with vacancy defects, introducing Li interstitials boosts the ionic conductivity of Li 3 OCl by 3 orders of magnitude. In addition to defect engineering, designing a three-dimensional diffusion pathway for Li ions enhances bulk ionic conductivity. While LaCl 3 -based electrolytes exhibit good compatibility with Li-metal electrodes, their intrinsic low ionic conductivity poses limitations. We propose constructing a three-dimensional diffusion pathway by connecting neighboring onedimensional channels through the introduction of La vacancies, significantly enhancing the ionic conductivity of LaCl...

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Section: Design Of Inorganic Solid Electrolytes With Enhanced Ionic C...mentioning

confidence: 99%

Computational Design of Inorganic Solid-State Electrolyte Materials for Lithium-Ion Batteries

Ma,

2024

Acc. Mater. Res.

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Effects of Grain Boundaries and Surfaces on Electronic and Mechanical Properties of Solid Electrolytes

Xie,

Deng,

Liu

et al. 2024

Advanced Energy Materials

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Extended defects, including exposed surfaces and grain boundaries (GBs), are critical to the properties of polycrystalline solid electrolytes in all‐solid‐state batteries (ASSBs). These defects can alter the mechanical and electronic properties of solid electrolytes, with direct manifestations in the performance of ASSBs. Here, by building a library of 590 surfaces and grain boundaries of 11 relevant solid electrolytes—including halides, oxides, and sulfides— their electronic, mechanical, and thermodynamic characteristics are linked to the functional properties of polycrystalline solid electrolytes. It is found that the energy required to mechanically “separate” grain boundaries can be significantly lower than in the bulk region of materials, which can trigger preferential cracking of solid electrolyte particles in the grain boundary regions. The brittleness of ceramic solid electrolytes, inferred from the predicted low fracture toughness at the grain boundaries, contributes to their cracking under local pressure imparted by lithium (sodium) penetration in the grain boundaries. Extended defects of solid electrolytes introduce new electronic interfacial states within bandgaps of solid electrolytes. These states alter and possibly increase locally the availability of free electrons and holes in solid electrolytes. Factoring effects arising from extended defects appear crucial to explain electrochemical and mechanical observations in ASSBs.

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Influence of Surfaces on Ion Transport and Stability in Antiperovskite Solid Electrolytes at the Atomic Scale

Dutra,

Quirk,

Zhou

et al. 2024

ACS Materials Lett.

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Antiperovskites are generating considerable interest as potential solid electrolyte materials for solid-state batteries because of their promising ionic conductivity, wide electrochemical windows, stability, chemical diversity and tunability, and low cost. Despite this, there is a surprising lack of a systematic study of antiperovskite surfaces and their influence on the performance of these materials in energy storage applications. This is rectified here by providing a comprehensive density functional theory investigation of the surfaces of M3OX (M = Li or Na; X = Cl or Br) antiperovskites. Specifically, we focus on the stability, electronic structure, defect chemistry, and ion transport properties of stable antiperovskite surfaces and how these contribute to the overall performance and suitability of these materials as solid electrolytes. The findings presented here provide critical insights for the design of antiperovskite surfaces that are both stable and promote ion transport in solid-state batteries.

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Going against the Grain: Atomistic Modeling of Grain Boundaries in Solid Electrolytes for Solid-State Batteries

Cited by 4 publications

References 86 publications

Computational Design of Inorganic Solid-State Electrolyte Materials for Lithium-Ion Batteries

Computational Design of Inorganic Solid-State Electrolyte Materials for Lithium-Ion Batteries

Effects of Grain Boundaries and Surfaces on Electronic and Mechanical Properties of Solid Electrolytes

Influence of Surfaces on Ion Transport and Stability in Antiperovskite Solid Electrolytes at the Atomic Scale

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