Superionic conductivity in lithium argyrodite solid-state electrolyte by controlled Cl-doping

Yu, Chuang; Li, Yong; Willans, Mathew J.; Zhao, Yang; Adair, Keegan R.; Zhao, Feipeng; Li, Weihan; Deng, Sixu; Liang, Jianwen; Banis, Mohammad Norouzi; Li, Ruying; Huang, Huan; Zhang, Li; Yang, Rong; Lu, Shigang; Huang, Yining; Sun, Xueliang

doi:10.1016/j.nanoen.2019.104396

Cited by 104 publications

(83 citation statements)

References 47 publications

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“…[17][18][19][20][21][22][23] The synthetic Li6PS5X lithiumargyrodites are derived by replacing silver with lithium and substituting one chalcogen per formula unit with a halide ion. A large number of lithium-argyrodite compositions have previously been synthesized, [24][25][26][27][28][29][30][31] with some of the highest room temperature ionic conductivities reported for the Li6+xP1-xGexS5I and Li6+xSb1-xSixS5I series. 32,33 This classification follows the nomenclature proposed by Deiseroth et al with symmetry labels referring to the inverted setting 2.…”

Section: Introductionmentioning

confidence: 99%

“…(anion-ordered) is a poor Li-ion conductor compared to Li6PS5Cl and Li6PS5Br (both aniondisordered), which exhibit ×10 3 higher room-temperature ionic conductivities. 9,13,[38][39][40] While the correlation between anion disorder and fast lithium transport is well documented, 9,[24][25][26][27][28][29][30][31][32][33]36,41 the effect of anion site-disorder on the microscopic dynamics and local structure of the mobile lithium ions is less well understood. In Li6PS5X argyrodites, the anionic framework contains 132 tetrahedral voids per unit cell (4 formula units) that may accommodate the corresponding 24 lithium ions.…”

Section: Introductionmentioning

confidence: 99%

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Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li₆PS₅X (X = Cl, Br, I)

et al. 2020

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The lithium-argyrodites Li 6 PS 5 X (X = Cl, Br, I) exhibit high lithium-ion conductivities, making them promising candidates for use in solid-state batteries. These solid electrolytes can show considerable substitutional X − /S 2− anion-disorder, with greater disorder typically correlated with higher lithium-ion conductivities. The atomic-scale effects of this anion site-disorder within the host lattice-in particular how lattice disorder modulates the lithium substructure-are not well understood. Here, we characterize the lithium substructure in Li 6 PS 5 X (X = Cl, Br, I) as a function of temperature and anion site-disorder, using Rietveld refinements against temperature-dependent neutron diffraction data. Analysis of these high-resolution diffraction data reveals an additional lithium position previously unreported for Li 6 PS 5 Xargyrodites, suggesting that the lithium conduction pathway in these materials differs from the most common model proposed in earlier studies. Analysis of the Li + positions and their radial distributions reveals that greater inhomogeneityof the local anionic charge, due to X − /S 2− site-disorder, is associated with more spatially-diffuse lithium distributions. This observed coupling of site-disorder and lithium distribution provides a possible explanation for the enhanced lithium transport in anion-disordered lithium argyrodites, and highlights the complex interplay between anion configuration and lithium substructure in this family of superionic conductors. File list (2) download file view on ChemRxiv revised manuscript.pdf (2.52 MiB) download file view on ChemRxiv Revised Supporting Information.pdf (1.35 MiB)

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li₆PS₅X (X = Cl, Br, I)

et al. 2020

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show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…39 This three-jump model, in which the lithium diffusion mechanism is described entirely in terms of movement between type 5 sites, has been widely applied to explain experimental and theoretical trends in lithium transport in Li6PS5X and related lithium-argyrodites. 9,[24][25][26][27][28][29][30][31][32]41,43 This model, however, ignores the role of non-type 5 tetrahedra, and therefore gives an incomplete description of the lithium diffusion pathways in the argyrodite structure. The type 5 tetrahedra form face-sharing pairs, and pure 5 → 5 lithium motion is only possible for the doublet jump.…”

Section: Introductionmentioning

confidence: 99%

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On the Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li6PS5X (X = Cl, Br, I)

Minafra¹,

Kraft²,

Bernges³

et al. 2020

Preprint

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The lithium-argyrodites Li6PS5X (X = Cl, Br, I) exhibit high lithium-ion conductivities, making them promising candidates for use in solid-state batteries. These solid electrolytes can show considerable substitutional X−/S2− anion-disorder, with greater disorder typically correlated with higher lithium-ion conductivities. The atomic-scale effects of this anion site-disorder within the host lattice—in particular how lattice disorder modulates the lithium substructure—are not well understood. Here, we characterize the lithium substructure in Li6PS5X (X = Cl, Br, I) as a function of temperature and anion site-disorder, using Rietveld refinements against temperature-dependent neutron diffraction data. Analysis of these high-resolution diffraction data reveals an additional lithium position previously unreported for Li6PS5Xargyrodites, suggesting that the lithium conduction pathway in these materials differs from the most common model proposed in earlier studies. Analysis of the Li+ positions and their radial distributions reveals that greater inhomogeneityof the local anionic charge, due to X−/S2− site-disorder, is associated with more spatially-diffuse lithium distributions. This observed coupling of site-disorder and lithium distribution provides a possible explanation for the enhanced lithium transport in anion-disordered lithium argyrodites, and highlights the complex interplay between anion configuration and lithium substructure in this family of superionic conductors.

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A High Air‐Stability and Li‐Metal‐Compatible Li_3+2xP_1−xBi_xS_4−1.5xO_1.5x Sulfide Electrolyte for All‐Solid‐State Li–Metal Batteries

Huang

Liu

et al. 2022

Adv Funct Materials

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All-solid-state batteries are one of the most promising lithium-ion batteries as they are safe with high energy density and applicable to different occasions. Sulfide solid electrolytes (SSEs) are welcoming due to their good ionic conductivity and processability. However, as the SSE conductor is unstable when exposed to air, its development and application are limited. A series of new Li 3+2x P 1−x Bi x S 4−1.5x O 1.5x (X = 0.02, 0.04, 0.06, 0.08) solid electrolytes are synthesized by co-doping Li 3 PS 4 with Bi and O, and the new electrolytes have better ionic conductivity and air-stability than Li 3 PS 4 . The lithium ionic conductivity of Li 3.12 P 0.94 Bi 0.06 S 3.91 O 0.09 solid electrolytes reached up to 2.8 mS cm -1 at room temperature, the highest and 9 times as high as that of Li 3 PS 4 . The doped solid electrolytes are compatible with lithium anode, and the cycling performance is improved. Importantly, the critical current density of Li 3.12 P 0.94 Bi 0.06 S 3.91 O 0.09 electrolytes can reach to 1.2 mA cm -2 . In particular, the Li|Li 3.12 P 0.94 Bi 0.06 S 3.91 O 0.09 |Li symmetric cells are stable even after 400 h running at 1 mA cm -2 and 25 °C. Bi 2 O 3 doping SSEs are expected to be the next generation of all-solid-state lithium batteries due to their good ionic conductivity and air-stability.

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Superionic conductivity in lithium argyrodite solid-state electrolyte by controlled Cl-doping

Cited by 104 publications

References 47 publications

Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li₆PS₅X (X = Cl, Br, I)

Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li₆PS₅X (X = Cl, Br, I)

On the Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li6PS5X (X = Cl, Br, I)

A High Air‐Stability and Li‐Metal‐Compatible Li_3+2xP_1−xBi_xS_4−1.5xO_1.5x Sulfide Electrolyte for All‐Solid‐State Li–Metal Batteries

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Superionic conductivity in lithium argyrodite solid-state electrolyte by controlled Cl-doping

Cited by 104 publications

References 47 publications

Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li6PS5X (X = Cl, Br, I)

Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li6PS5X (X = Cl, Br, I)

On the Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li6PS5X (X = Cl, Br, I)

A High Air‐Stability and Li‐Metal‐Compatible Li3+2xP1−xBixS4−1.5xO1.5x Sulfide Electrolyte for All‐Solid‐State Li–Metal Batteries

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Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li₆PS₅X (X = Cl, Br, I)

Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li₆PS₅X (X = Cl, Br, I)

A High Air‐Stability and Li‐Metal‐Compatible Li_3+2xP_1−xBi_xS_4−1.5xO_1.5x Sulfide Electrolyte for All‐Solid‐State Li–Metal Batteries