Air-stable Li<sub>3</sub>InCl<sub>6</sub> electrolyte with high voltage compatibility for all-solid-state batteries

Li, Xiaona; Liang, Jianwen; Luo, Jing; Banis, Mohammad Norouzi; Wang, Changhong; Li, Weihan; Deng, Sixu; Yu, Chuang; Zhao, Feipeng; Hu, Yongfeng; Sham, Tsun‐Kong; Zhang, Li; Zhao, Shangqian; Lu, Shigang; Huang, Huan; Li, Ruying; Adair, Keegan R.; Sun, Xueliang

doi:10.1039/c9ee02311a

Cited by 455 publications

(513 citation statements)

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“…Our calculated Li-ion conductivity of Li 3 InCl 6 (C2/m) is 1.2 mS cm −1 , in good agreement with the experimental reported value of 1.49 mS cm −1 . [18,[21][22][23] A recent experiment study reports Li-ion conductivity of Li 3 YCl 6 to be 0.51 mS cm −1 , which is slightly lower than our calculated Li-ion conductivity of 14 mS cm −1 , with error bounds in the range of 5 to 47 mS cm −1 and the difference may be attributed to the existence of grain boundary [18] and blocking defects. [19] In addition, a wide range of Zr-doped Li (Figure 2e).…”

Section: High-throughput Computation Of Chloride Li-ion Conductorscontrasting

confidence: 84%

“…Our results further confirm recent computation and experimental studies that Li 3 MCl 6 are promising Li SICs for a wide range of cation and substitutions. [18][19][20][21][22][23][24][25] Most Li x MCl 4 and Li x M 1/2 Cl 4 materials even with substantial levels of substitution have Li-ion conductivities much lower than 200 mS cm −1 at 600 K, and 24 of 51 materials exhibit a negligible amount of Li-ion hopping to obtain a statistically reliable ionic diffusivity. There are a few Li-ion conductors as the exceptions in the Li x MCl 4 category, as a result of their distinct local cation coordination, which are further discussed in Section 3.…”

Section: High-throughput Computation Of Chloride Li-ion Conductorsmentioning

confidence: 99%

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Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors

Liu

Wang

Nolan

et al. 2020

Advanced Energy Materials

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Only a limited number of materials systems have been demonstrated as Li SICs, including Li 10 GeP 2 S 12 (LGPS), [4] garnet Li 7 La 3 Zr 2 O 12 (LLZO), [9,10] and NASICON Li 1.3 Al 0.3 Ti 1.7 (PO 4) 3 (LATP). [11] However, these Li SICs do not have all properties required for ASSLBs. Compared to oxide SICs, sulfide SICs have desired mechanical deformability for forming good interface physical contacts in ASSLB cell assembly, but have narrow electrochemical window, [12,13] poor cathode interface compatibility, [14-16] and poor air/ moisture stability, [5,17] which impede the large-scale commercialization of sulfidebased ASSLBs. Asano et al. discovered Li 3 YCl 6 (LYC) and Li 3 YBr 6 (LYB) as new Li SICs with high Li-ion conductivities on the order of 1 mS cm −1 at RT and with good ASSLB cell performances. [18] In addition to the desired deformable mechanical properties as sulfides, first-principles computation studies [17,19] confirmed that the chloride chemistry in general gives a lower barrier for Li-ion migration, wider electrochemical window, good interface compatibility with cathode, and good air/moisture stability compared to sulfide SEs. With a combination of multiple desired properties, lithium halides, particularly chlorides, are a promising class of Li SICs for SEs in ASSLBs. The chloride anion chemistry is advantageous for Li-ion migration, thanks to the relatively large anion radius, large anion polarizability, and weak interaction with Li-ion. [18-20] Firstprinciples computation confirms that Li-ion migration exhibits a low energy barrier of 0.28 eV in face-centered cubic (fcc) and of 0.29 eV in hexagonal close packed (hcp) Cl − anion sublattices with no cation under typical lattice volume of lithium chlorides. [19] Recent experimental studies reported a series of Licontaining chlorides Li 3 MCl 6 (M = In, Er, Sc) and their doped variations that achieved Li-ion conductivities on the order of 1 mS cm −1 at RT. [19,21-25] While the discovery of new SIC systems in oxides and sulfides is greatly limited by the unique crystal structures required for achieving fast Li-ion conduction, [26-28] Li-containing chlorides with common fcc and hcp anion sublattices exhibit adequately low Li-ion migration barrier, and are a promising chemical space for new Li-ion conductors. A systematic fundamental understanding of chloride Li-ion conductors is essential for guiding the discovery and design new Li-containing chloride SICs. While Li-containing chlorides are common in close-packed fcc and hcp anion sublattices, they All-solid-state Li-ion batteries require Li-ion conductors as solid electrolytes (SEs). Li-containing halides are emerging as a promising class of lithium-ion conductors with good electrochemical stability and other properties needed for SEs in all-solid-state batteries. Compared to oxides and sulfides, Li-ion diffusion mechanisms in Li-containing halides are less well understood, in particular regarding the effects of Li content and cation sublattices, which can be tailored for improving Li-ion conduction...

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Section: High-throughput Computation Of Chloride Li-ion Conductorscontrasting

confidence: 84%

Section: High-throughput Computation Of Chloride Li-ion Conductorsmentioning

confidence: 99%

Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors

Liu

Wang

Nolan

et al. 2020

Advanced Energy Materials

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“…Challenged by the oxidative instability of the thiophosphate‐based electrolyte, recently, the rare‐earth halides Li 3 YX 6 (X = Cl, Br) have attracted interest as they exhibit high ionic conductivity on the order of 1 mS cm −1 and have been reported to exhibit an enhanced oxidative stability to higher potentials . In addition, by combining multiple descriptors for fast ionic motion along with the need for high stability, Li 3 ErCl 6 , Li 3 LaI 6 , and Li 3 InCl 6 were found to exhibit a high ionic conductivity. However, none of these materials are novel in itself as the work on the A 3 InCl 6 ( A = Na, K, Ag, Tl) systems dates back as far as 1967 .…”

Section: Introductionmentioning

confidence: 99%

“…Inspired by the fast ion transport, the clear but not yet understood influence of the synthesis methods on the ionic transport, and the open question of Y/Er site disorder, here we investigate the influence of the synthesis on the local structure and with it the resulting ionic transport properties. Using a combination of X‐ray diffraction, X‐ray pair distribution function (PDF) analysis, impedance spectroscopy, and density functional theory (DFT), we show the direct influence of the synthesis methods on the local structure and transport properties.…”

Section: Introductionmentioning

confidence: 99%

Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li₃MCl₆ (M = Y, Er) Superionic Conductors

Schlem

Muy

Prinz

et al. 2019

Advanced Energy Materials

233

402

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The lithium‐conducting, rare‐earth halides, Li3MX6 (M = Y, Er; X = Cl, Br), have garnered significantly rising interest recently, as they have been reported to have oxidative stability and high ionic conductivities. However, while a multitude of materials exhibit a superionic conductivity close to 1 mS cm−1, the exact design strategies to further improve the ionic transport properties have not been established yet. Here, the influence of the employed synthesis method of mechanochemical milling, compared to subsequent crystallization routines as well as classic solid‐state syntheses on the structure and resulting transport behavior of Li3ErCl6 and Li3YCl6 are explored. Using a combination of X‐ray diffraction, pair distribution function analysis, density functional theory, and impedance spectroscopy, insights into the average and local structural features that influence the underlying transport are provided. The existence of a cation defect within the structure in which Er/Y are disordered to a new position strongly benefits the transport properties. A synthetically tuned, increasing degree of this disordering leads to a decreasing activation energy and increasing ionic conductivity. This work sheds light on the possible synthesis strategies and helps to systematically understand and further improve the properties of this class of materials.

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“…In the past several decades, various SSEs have been extensively explored. [ 26–32 ] Among them, garnet‐type SSEs have attracted tremendous interest due to their high ionic conductivity, chemical stability, and superior stability against LMA. [ 33–38 ] Unfortunately, the garnet suffers from poor wettability with LMA that the LMA/garnet interface presents a large resistance.…”

Section: Introductionmentioning

confidence: 99%

Shaping the Contact between Li Metal Anode and Solid‐State Electrolytes

Duan

Huang

Wang

et al. 2020

Adv Funct Materials

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Scientific and technological interest in solid-state Li metal batteries (SSLMBs) arises from their excellent safety and promising high energy density. However, the practical application of SSLMBs is hindered by poor contact between the Li metal anode (LMA) and solid-state electrolytes (SSEs). To circumvent this limitation, a pattern-guided approach that shapes the LMA/SSE contact is disclosed to offer fast Li ion conduction in the interface. A thermallytreated copper foam is used as the lithophilic pattern to confine and guide Li for forming a tight contact with garnet-type SSE. The contact can be easily manipulated according to the shape of lithiophilic pattern, facilitating cell assembly. The resulting Li|patterned garnet|Li symmetric cell exhibits an interfacial resistance of 9.8 Ω cm 2 , which is dramatically lower than that of 998 Ω cm 2 for Li|pristine garnet|Li symmetric cell. Being used in Li-sulfur batteries, the patterned garnet effectively eliminates the polysulfide shuttle and enables stable cycling performance, showing a low capacity decay of 0.035% per cycle over 1000 cycles. The fundamental contact process of metallic anodes/SSEs is carefully investigated. This contact strategy provides a new design concept to improve the interface wettability via a lithiophilic pattern for a variety of SSEs that cannot wet with metallic anodes.

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Air-stable Li₃InCl₆ electrolyte with high voltage compatibility for all-solid-state batteries

Abstract: Ambient-air-stable Li3InCl6 halide solid electrolyte, with high ionic conductivity of 1.49 × 10−3 S cm−1 at 25 °C, delivers essential advantages over commercial sulfide-based solid electrolyte.

Cited by 455 publications

References 40 publications

Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors

Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors

Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li₃MCl₆ (M = Y, Er) Superionic Conductors

Shaping the Contact between Li Metal Anode and Solid‐State Electrolytes

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Air-stable Li3InCl6 electrolyte with high voltage compatibility for all-solid-state batteries

Abstract: Ambient-air-stable Li3InCl6 halide solid electrolyte, with high ionic conductivity of 1.49 × 10−3 S cm−1 at 25 °C, delivers essential advantages over commercial sulfide-based solid electrolyte.

Cited by 455 publications

References 40 publications

Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors

Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors

Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li3MCl6 (M = Y, Er) Superionic Conductors

Shaping the Contact between Li Metal Anode and Solid‐State Electrolytes

Contact Info

Product

Resources

About

Air-stable Li₃InCl₆ electrolyte with high voltage compatibility for all-solid-state batteries

Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li₃MCl₆ (M = Y, Er) Superionic Conductors