Elucidating the nature of grain boundary resistance in lithium lanthanum titanate

Symington, Adam; Molinari, Marco; Dawson, James A.; Statham, Joel; Purton, John A.; Canepa, Pieremanuele; Parker, Stephen C.

doi:10.1039/d0ta11539h

Cited by 53 publications

(48 citation statements)

References 74 publications

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“…Local structural deviation such as short-range order has been investigated by a neutron scattering technique in which a La-poor layer forms a wide-open 2D grid for Li + transportation . The presence of grain boundaries (GBs) in the pellet has long been recognized ,, to lower the ion conduction by at least one order of magnitude. The origin of the low GB conductivity is believed to be chemical variation at the GBs either related to the positively charged space-charge layer or the formation of a binary Ti–O compound, both of which prohibit the abundance and transport of the Li-ions.…”

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Atomic Defect Mediated Li-Ion Diffusion in a Lithium Lanthanum Titanate Solid-State Electrolyte

Zhang

Nian

et al. 2022

ACS Nano

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Lithium lanthanum titanium oxide (LLTO) as a fast Li-ion conductor is a promising candidate for future all-solid-state Li batteries. Fundamental understanding of the microstructure of LLTO and its effect on the Li+ diffusion mechanism, especially across different length scales and interfaces, is a prerequisite to improving the material design and processing development of oxide-based solid electrolytes. Herein, through detailed structural analysis of LLTO ceramic pellets by aberration-corrected transmission electron microscopy, we discovered previously unreported intrinsic planar defects in LLTO single-crystal grains. These planar defects feature an antiphase boundary along specific crystal planes with a “rock-salt” structure enriched by Li within a few atomic layers. Corroborated by density-functional-theory-based calculations, we show an increased diffusion barrier across these planar defects inevitably lowers the bulk Li+ diffusivity of the oxide electrolyte.

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Atomic Defect Mediated Li-Ion Diffusion in a Lithium Lanthanum Titanate Solid-State Electrolyte

Zhang

Nian

et al. 2022

ACS Nano

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“…Especially, the Li-ion conductivity at the GB has been revealed using the classical simulation methods. [19,23,38,39] Especially for LLZO, this method has indicated that the GB resistance is sensitive to the GB structure and temperature. [23] Firstprinciples simulation based on the atomistic model as a powerful way can provide comprehensive results about the properties of SE.…”

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confidence: 99%

“…[13][14][15][16][17] As most of the synthesized SEs are polycrystalline, the grain boundary (GB) has an inevitable influence on their performances. [18,19] However, until now, this underlying GB effect has not been thoroughly understood yet. For example, numerous works have reported the resistance at GB related to the decrease in the ion conductivity in LLZO, [20][21][22][23] while some other studies have observed contradictory results, where the sample with small grain size has higher conductivity than that containing large-sized grains, indicating the faster ion transport at the GBs.…”

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confidence: 99%

Revealing Atomic‐Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li₇La₃Zr₂O₁₂ Solid Electrolyte

Gao

Jalem

Tian

et al. 2021

Advanced Energy Materials

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electric vehicles. [1,2] Due to the existence of weakness of the organic liquid electrolyte in the traditional Li-ion battery (e.g., flammable), all-solid-state battery (ASSB) containing an inorganic solid electrolyte is one of the most promising candidates of the next-generation battery owing to its improved safety and cycle stability. [3][4][5] Through the long-term development, a variety of high-performance solid electrolytes (SEs) has been successfully synthesized, whose ion conductivities are comparable with the traditional liquid electrolytes. [6][7][8][9] Among of them, the garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) as a superior solid electrolyte has attracted great interest, [8,10,11] owing to its high conductivity (≈10 -4 S cm −1 ), wide electrochemical window (≈6 eV). [12] More promisingly, LLZO shows a good compatibility with the ultimate anode material, Li metal, to achieve an ASSB with a significantly high energy density. [13][14][15][16][17] As most of the synthesized SEs are polycrystalline, the grain boundary (GB) has an inevitable influence on their performances. [18,19] However, until now, this underlying GB effect has not been thoroughly understood yet. For example, numerous works have reported the resistance at GB related to the decrease in the ion conductivity in LLZO, [20][21][22][23] while some other studies have observed contradictory results, where the sample with small grain size has higher conductivity than that containing large-sized grains, indicating the faster ion transport at the GBs. [24][25][26] Moreover, GBs are expected to contribute to the Li dendrite growth in LLZO, [27][28][29] which leads to the short-circuiting of the cell. [24,[30][31][32][33] It is reported that the inhomogeneous depletion and low ion conductivity at the GB are responsible for the dendrite growth. [32,34] Particularly, recent works have proposed that the dendrite propagation originates from the high electronic conductivity, [30,35] which is reported to be appeared at the GB. [36,37] Fully unraveling these serious GB issues require a comprehensive understanding of the ion diffusion, defect chemistry, and electronic properties at GB. Especially, the Li-ion conductivity at the GB has been revealed using the classical simulation methods. [19,23,38,39] Especially for LLZO, this method has indicated that the GB resistance is sensitive to the GB structure and temperature. [23] Firstprinciples simulation based on the atomistic model as a powerful way can provide comprehensive results about the properties of SE. Especially for LLZO, it has been extensively used to explain the phase transition, [40] migration mechanism, [41] electrochemical window, [12] defect chemistry, [42] and the phenomena on the surface and at the interface with Li metal. [43,44] Unfortunately, as far as we For real applications of all-solid-state batteries (ASSBs) to be realized, understanding and control of the grain boundaries (GBs) are essential. However, the in-depth insight into the atomic-scale defect stabilities and transport of ions aro...

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“…The demand for advanced energy storage systems has increased dramatically over the past few decades due to the development of portable electronic devices and the electric vehicle industry. 1–3 Lithium-ion batteries (LIBs) have been widely studied because of their superior performance to other energy storage devices. 4,5 However, there are many problems in commercial LIBs containing liquid electrolytes, such as difficulty in further improving their energy density and poor safety.…”

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confidence: 99%

Hydrogen bonding enhanced SiO₂/PEO composite electrolytes for solid-state lithium batteries

et al. 2022

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Elucidating the nature of grain boundary resistance in lithium lanthanum titanate

Abstract: Solid electrolytes for all-solid-state batteries are generating remarkable research interest as a means to improve, their safety, stability and performance. Solid electrolytes are often polycrystalline and the effect that grain...

Cited by 53 publications

References 74 publications

Atomic Defect Mediated Li-Ion Diffusion in a Lithium Lanthanum Titanate Solid-State Electrolyte

Atomic Defect Mediated Li-Ion Diffusion in a Lithium Lanthanum Titanate Solid-State Electrolyte

Revealing Atomic‐Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li₇La₃Zr₂O₁₂ Solid Electrolyte

Hydrogen bonding enhanced SiO₂/PEO composite electrolytes for solid-state lithium batteries

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Elucidating the nature of grain boundary resistance in lithium lanthanum titanate

Abstract: Solid electrolytes for all-solid-state batteries are generating remarkable research interest as a means to improve, their safety, stability and performance. Solid electrolytes are often polycrystalline and the effect that grain...

Cited by 53 publications

References 74 publications

Atomic Defect Mediated Li-Ion Diffusion in a Lithium Lanthanum Titanate Solid-State Electrolyte

Atomic Defect Mediated Li-Ion Diffusion in a Lithium Lanthanum Titanate Solid-State Electrolyte

Revealing Atomic‐Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid Electrolyte

Hydrogen bonding enhanced SiO2/PEO composite electrolytes for solid-state lithium batteries

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Revealing Atomic‐Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li₇La₃Zr₂O₁₂ Solid Electrolyte

Hydrogen bonding enhanced SiO₂/PEO composite electrolytes for solid-state lithium batteries