Tuning ionic conductivity and electrode compatibility of Li3YBr6 for high-performance all solid-state Li batteries

Yu, Chuang; Li, Yong; Adair, Keegan R.; Li, Weihan; Zhao, Yang; Willans, Mathew J.; Thijs, Michel; Wang, Changhong; Zhao, Feipeng; Sun, Qian; Deng, Sixu; Liang, Jianwen; Li, Xiaona; Li, Ruying; Sham, Tsun‐Kong; Huang, Huan; Lu, Shigang; Zhao, Shangqian; Zhang, Li; Eijck, Lambert van; Huang, Yining; Sun, Xueliang

doi:10.1016/j.nanoen.2020.105097

Cited by 54 publications

(51 citation statements)

References 31 publications

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“…[11] First cell studies show good stability of the halide SEs in contact with CAMs such as LiCoO 2 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 ,a nd side reactions with the CAMs were not reported. [8][9][10][11]15] This is in accordance with theoretical predictions that suggest high oxidation stability of the halide anions. [7,14] According to theoretical predictions, the electrochemical stability windows (ESW) of Li 3 InCl 6 and Li 3 YCl 6 are 2.38-4.26 Vand 0.62-4.02 vs.L i + /Li, respectively, [14] showing that these electrolytes can be used in contact with most CAMs but that the anode interface may be unstable.D ue to the expected instability against the LMA, al ithium thiophosphate separator electrolyte is mostly used, and the halide SEs are primarily used as cathode electrolyte.…”

Section: Introductionsupporting

confidence: 91%

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

et al. 2021

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Owing to high ionic conductivity and good oxidation stability, halide‐based solid electrolytes regain interest for application in solid‐state batteries. While stability at the cathode interface seems to be given, the stability against the lithium metal anode has not been explored yet. Herein, the formation of a reaction layer between Li3InCl6 (Li3YCl6) and lithium is studied by sputter deposition of lithium metal and subsequent in situ X‐ray photoelectron spectroscopy as well as by impedance spectroscopy. The interface is thermodynamically unstable and results in a continuously growing interphase resistance. Additionally, the interface between Li3InCl6 and Li6PS5Cl is characterized by impedance spectroscopy to discern whether a combined use as cathode electrolyte and separator electrolyte, respectively, might enable long‐term stable and low impedance operation. In fact, oxidation stable halide‐based lithium superionic conductors cannot be used against Li, but may be promising candidates as cathode electrolytes.

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Section: Introductionsupporting

confidence: 91%

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

et al. 2021

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“…24,25,35 The differences in conductivity may stem from the varying synthesis parameters and 16 annealing times that were applied, since it is known for the halide materials that synthesis conditions have a severe influence on structure and properties. 29,31,32,50 In addition, the small conductivity discrepancy may also be due to the known interlaboratory deviations in the ionic conductivity of these mechanically soft materials. 51 The activation energy determined by impedance spectroscopy reaches a minimum for Li2.6In0.6Zr0.4Cl6 which coincides with the optimum of the conductivity found here.…”

Section: Ionic Transportmentioning

confidence: 99%

Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li3-xIn1-xZrxCl6 (0 ≤ X ≤ 0.5)

Helm¹,

Schlem²,

Wankmiller³

et al. 2021

Preprint

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In recent years, ternary halides Li3MX6 (M = Y, Er, In; X = Cl, Br, I) have garnered attention as solid electrolytes due to their wide electrochemical stability window and favorable room-temperature conductivities. In this material class, the influences of iso- or aliovalent substitutions are so far rarely studied in-depth, despite this being a common tool for correlating structure and transport properties. In this work, we investigate the impact of Zr substitution on the structure and ionic conductivity of Li3InCl6 (Li3-xIn1-xZrxCl6 with 0 ≤ x ≤ 0.5) using a combination of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy. Analysis of high-resolution diffraction data shows the presence of an additional tetrahedrally coordinated lithium position together with cation site-disorder, both of which have not been reported previously for Li3InCl6. This Li+ position and cation disorder lead to the formation of a three-dimensional lithium ion diffusion channel, instead of the expected two-dimensional diffusion. Upon Zr4+ substitution, the structure exhibits non-uniform volume changes along with an increasing number of vacancies, all of which lead to an increasing ionic conductivity in this series of solid solutions.

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“…29,31 Moreover, studies showed that the heat treatment conditions strongly influence the ionic conductivity. 31,32 Just recently, Kwak et al showed that a mechanochemical synthesis stabilizes the trigonal structure for Li2ZrCl6, while annealing resulted in a monoclinic structure exhibiting conductivities of 0.4 mS•cm -1 and 5.7 • 10 -3 mS•cm -1 , respectively. 33 The conductivity of mechanochemically prepared Li2ZrCl6 was further enhanced up to ~ 1 mS•cm -1 by Fe 3+ substitution.…”

Section: Introductionmentioning

confidence: 99%

Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li_3–xIn_1–xZr_xCl₆ (0 ≤ x ≤ 0.5)

et al. 2021

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In recent years, ternary halides Li3MX6 (M = Y, Er, In; X = Cl, Br, I) have garnered attention as solid electrolytes due to their wide electrochemical stability window and favorable roomtemperature conductivities. In this material class, the influences of iso-or aliovalent substitutions are so far rarely studied in-depth, despite this being a common tool for correlating structure and transport properties. In this work, we investigate the impact of Zr substitution on the structure and ionic conductivity of Li3InCl6 (Li3-xIn1-xZrxCl6 with 0 ≤ x ≤ 0.5) using a combination of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy.Analysis of high-resolution diffraction data shows the presence of an additional tetrahedrally coordinated lithium position together with cation site-disorder, both of which have not been reported previously for Li3InCl6. This Li + position and cation disorder lead to the formation of a three-dimensional lithium ion diffusion channel, instead of the expected two-dimensional diffusion. Upon Zr 4+ substitution, the structure exhibits non-uniform volume changes along with an increasing number of vacancies, all of which lead to an increasing ionic conductivity in this series of solid solutions.

show abstract

Tuning ionic conductivity and electrode compatibility of Li3YBr6 for high-performance all solid-state Li batteries

Cited by 54 publications

References 31 publications

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li3-xIn1-xZrxCl6 (0 ≤ X ≤ 0.5)

Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li_3–xIn_1–xZr_xCl₆ (0 ≤ x ≤ 0.5)

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Tuning ionic conductivity and electrode compatibility of Li3YBr6 for high-performance all solid-state Li batteries

Cited by 54 publications

References 31 publications

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li3-xIn1-xZrxCl6 (0 ≤ X ≤ 0.5)

Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li3–xIn1–xZrxCl6 (0 ≤ x ≤ 0.5)

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Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li_3–xIn_1–xZr_xCl₆ (0 ≤ x ≤ 0.5)