Heat treatment protocol for modulating ionic conductivity via structural evolution of Li3-xYb1-xMxCl6 (M = Hf4+, Zr4+) new halide superionic conductors for all-solid-state batteries

Park, Juhyoun; Han, Daseul; Kwak, Hiram; Han, Yoonjae; Choi, Yong Jeong; Nam, Kyung Wan; Jung, Yoon Seok

doi:10.1016/j.cej.2021.130630

Cited by 82 publications

(114 citation statements)

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“…The anion arrangements of these halide SEs can be categorized into hcp and ccp structures. , For the hcp anion sublattice, there are two distinct crystal structures, the trigonal structure of Li 3 ErCl 6 (space group of P 3̅ m 1) and orthorhombic structure of Li 3 YbCl 6 (space group of Pnma ) (Figure a) . The Li 3 MCl 6 , with central metal M of Tb–Tm and Y with similar ionic radius of Er, has an hcp trigonal structure, and Li 3 LuCl 6 has an hcp orthorhombic structure as Li 3 YbCl 6 . ,, For ccp anion sublattice, there are spinel Li 2 Sc 2/3 Cl 4 (space group of Fd 3̅ m ) and monoclinic Li 3 ErBr 6 (space group of C 2/ m ). While Li 3 MCl 6 chlorides can form either hcp anion sublattice (M = Er, Y, Yb, etc.)…”

Section: Structure and Ionic Conductivity Of Halide Sesmentioning

confidence: 99%

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Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications

et al. 2022

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Recently, halide superionic conductors have emerged as promising solid electrolyte (SE) materials for all-solid-state batteries (ASSBs), owing to their inherent properties combining high Li + conductivity, good chemical and electrochemical oxidation stabilities, and mechanical deformability, compared to sulfide or oxide SEs. In this Review, recent advances in halide Li + -and Na + -conducting SEs are comprehensively summarized. After introducing the ionic diffusion mechanism and related governing factors of the crystal structures, we discuss the design strategies, such as the substitution and synthesis protocols, of the halide materials for further improving their properties. We review theoretical and experimental results on electrochemical stabilities and compatibilities with electrode materials. Moreover, we offer a critical assessment of the challenges and issues associated with the development of practical ASSB applications, such as cost considerations, stabilities in atmospheric air, aqueous solutions, and slurryprocessing, and the wet-slurry or dry fabrication of sheet-type electrodes (or SE membranes) for large-format ASSBs. Based on these discussions, we provide a perspective on the future research directions of halide SEs, emphasizing the need for expanding the materials space.

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Section: Structure and Ionic Conductivity Of Halide Sesmentioning

confidence: 99%

Section: Structure and Ionic Conductivity Of Halide Sesmentioning

confidence: 99%

Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications

et al. 2022

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“…In contrast to sulfide-based SEs, those with a chloride anion sublattice exhibit thermodynamic oxidation potentials well above this range – typically ∼4.2–4.3 vs. Li + /Li – and exhibit good conductivity of 1–2 mS cm −1 at room temperature, which makes them a promising choice as catholyte while still leaving room for further improvement. 23–29…”

Section: Introductionmentioning

confidence: 99%

Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

Nazar

Kochetkov

Zuo

et al. 2022

Energy Environ. Sci.

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“…Several other compositions were subsequently studied, including Li 3 InCl 6 , 32 Li 3 Y(Br 3 Cl 3 ), 33 Li x ScCl 3+x , 34 Li 3−x M 1−x Zr x Cl 6 (M = Y, Er), 35 and Li 3−x Yb 1−x M x Cl 6 (M = Hf 4+ , Zr 4+ ). 36 Na analogues are less explored, and only a few compositions [Na 3−x Er 1−x Zr x Cl 6 , 37 Na 2 ZrCl 6 , 38 Na 3 MCl 6 (M = Y, Er), and Na 3−x M 1−x Zr x Cl 6 (M = Y, Er)] 39,40 have been reported so far. Recently, Na 3 MCl 6 was systematically screened by Yu's group 41 with regard to its phase stability, electrochemical stability, and transport properties using density functional theory (DFT) calculations.…”

Section: ■ Introductionmentioning

confidence: 99%

Computational Screening of Na₃MBr₆ Compounds as Sodium Solid Electrolytes

Liu

et al. 2022

Chem. Mater.

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All-solid-state batteries (ASSBs) based on metallic Na have received an upsurge of interest in the past few years owing to the low cost of Na resources combined with enhanced safety compared to conventional liquid lithium-ion batteries. Solid electrolytes (SEs) serve as the central of ASSBs as they, together with the composite cathode layer, largely determine the power density, energy density, and cycling performance of ASSBs. Among the several categories of SE materials, halides are considered one of the most promising candidates due to their favorable combination of high ionic conductivity and chemical/electrochemical stability against high-voltage cathode materials. Excellent examples have been demonstrated by lithium halides, while their sodium counterparts have been less explored. Herein, we evaluate the phase stability, electrochemical stability, and conducting property of a series of Na-based bromides Na 3 MBr 6 with the joint utilization of density functional theory calculations, the bond valence site energy (BVSE) method, and ab initio molecular dynamics (AIMD) simulations. Our computations reveal that Na 3 MBr 6 could crystallize in three structures, trigonal P3̅ 1c, monoclinic P2 1 /n, and trigonal R3̅ phases, with the structural preference highly related to the type and ionic radii of the M cations. The BVSE and AIMD suggest that the P3̅ 1c phase exhibits a higher conductivity and lower migration barrier than P2 1 /n and R3̅ phases. With the introduction of Na vacancies, a significant enhancement in the conductivity was achieved, giving rise to a high extrapolated conductivity of 0.70 mS cm −1 at room temperature. In addition, the thermodynamic stability and chemical stability against cathode materials were also assessed. Our work provides insights into the fundamental understanding of sodium bromides and points to the importance of this family of materials to be used as potential candidates for SE materials in ASSBs.

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Heat treatment protocol for modulating ionic conductivity via structural evolution of Li3-xYb1-xMxCl6 (M = Hf4+, Zr4+) new halide superionic conductors for all-solid-state batteries

Cited by 82 publications

References 56 publications

Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications

Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications

Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

Computational Screening of Na₃MBr₆ Compounds as Sodium Solid Electrolytes

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Heat treatment protocol for modulating ionic conductivity via structural evolution of Li3-xYb1-xMxCl6 (M = Hf4+, Zr4+) new halide superionic conductors for all-solid-state batteries

Cited by 82 publications

References 56 publications

Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications

Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications

Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

Computational Screening of Na3MBr6 Compounds as Sodium Solid Electrolytes

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Computational Screening of Na₃MBr₆ Compounds as Sodium Solid Electrolytes