Li+ conduction in air-stable Sb-Substituted Li4SnS4 for all-solid-state Li-Ion batteries

Kwak, Hiram; Park, Kern Ho; Han, Daseul; Nam, Kyung‐Wan; Kim, Hyungsub; Jung, Yoon Seok

doi:10.1016/j.jpowsour.2019.227338

Cited by 86 publications

(81 citation statements)

References 55 publications

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“…To explain this, several factors could be considered: i) insufficient amount of mobile charge carriers of Li + , ii) strong Coulombic repulsion between Zr 4+ and Li + , which may lead to a higher activation barrier for Li + transport, and iii) reduced volume of Li + channels. [26,43] It should be noted that HT-Li 2 ZrCl 6 exhibited a smaller lattice volume (417.458 Å 3 ) than both Li 3 InCl 6 (426.409 Å 3 ) and Li 3 ScCl 6 (420.730 Å 3 ). [32,36] Specifically, based on the XRD data for Li 3 InCl 6 , while HT-Li 2 ZrCl 6 showed a marginal peak shift at ≈16.0° and ≈16.7° corresponding to the (020) and (110) planes, a noticeable peak shift occurred at ≈15° corresponding mainly to the (001) plane; this indicates asymmetric shrinkage of the lattice volume along the c axis ( Figure S7, Supporting Information).…”

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confidence: 99%

“…The increase in Li + conductivity (or decrease in activation energy) of Li 2+x Zr 1−x Fe x Cl 6 from x = 0.00 to x = 0.25 could be interpreted as the positive effect of the aliovalent substitution of Fe 3+ in the lattice. [26,44,[55][56][57] In contrast, the subsequent decrease in Li + conductivity (or increase in activation energy) is caused by the segregation of insulating LiCl. Specifically, the maximum Li + conductivity reached 0.98 mS cm −1 with the lowest activation energy of 0.346 eV for x = 0.25.…”

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confidence: 99%

“…Quantitative structural analysis using PDF measurements and/or density functional theory calculations could be effective for further investigations. [16,19,26,34,44,61,62] Nevertheless, several important insights on underlying mechanisms could be deduced. First, the aliovalent substitution increasing the amount of Li + could raise the concentration of effective charge carriers, which universally occurs in solid-state ionics.…”

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New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe³⁺‐Substituted Li₂ZrCl₆

Kwak

Han

Lyoo

et al. 2021

Advanced Energy Materials

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177

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, 0.7Li(CB 9 H 10)−0.3Li(CB 11 H 12), 6.7 mS cm −1), [11,12] and halides (e.g., Li 3 YX 6 [X = Cl, Br], 0.51-1.7 mS cm −1). [13,14] Thus far, oxide and sulfide SEs have been the most commonly investigated candidates. However, their pros and cons counteract each other. Oxide SEs possess high intrinsic electrochemical oxidation stabilities and relatively acceptable chemical stabilities; however, owing to their brittle nature, it is difficult to integrate them in devices. [3,10,15-17] On the other hand, the most important advantage of sulfide SEs, that is, mechanical deformability, which enables scalable cold-pressing-based fabrication protocols, is offset by their poor (electro)chemical stabilities. [3,16,18-20] On exposing sulfide SEs to humid air, the evolution of toxic H 2 S gases occurs. [21-26] Moreover, sulfide SEs exhibit oxidative decomposition at <3 V (vs Li/Li +) and are also incompatible with conventional layered LiMO 2 (M = Ni, Co, Mn, and Al) cathodes. [16,19,27] This issue can be alleviated by using protective coatings, such as LiNbO 3 and Li 3−x B 1−x C x O 3 ; [7,27] however, this constitutes additional processing costs. Furthermore, the oxidative decomposition of sulfide SEs at the surface of conductive carbon additives is unavoidable. [28-31] Recently, through reinvestigations on halide SEs, several compounds exhibiting Li + conductivities exceeding 10 −4 S cm −1 have been identified. [13,32−36] Asano and coworkers reported that trigonal Li 3 YCl 6 and monoclinic Li 3 YBr 6 showed high Li + Owing to the combined advantages of sulfide and oxide solid electrolytes (SEs), that is, mechanical sinterability and excellent (electro)chemical stability, recently emerging halide SEs such as Li 3 YCl 6 are considered to be a game changer for the development of all-solid-state batteries. However, the use of expensive central metals hinders their practical applicability. Herein, a new halide superionic conductors are reported that are free of rare-earth metals: hexagonal close-packed (hcp) Li 2 ZrCl 6 and Fe 3+-substituted Li 2 ZrCl 6 , derived via a mechanochemical method. Conventional heat treatment yields cubic close-packed monoclinic Li 2 ZrCl 6 with a low Li + conductivity of 5.7 × 10 −6 S cm −1 at 30 °C. In contrast, hcp Li 2 ZrCl 6 with a high Li + conductivity of 4.0 × 10 −4 S cm −1 is derived via ball-milling. More importantly, the aliovalent substitution of Li 2 ZrCl 6 with Fe 3+ , which is probed by complementary analyses using X-ray diffraction, pair distribution function, X-ray absorption spectroscopy, and Raman spectroscopy measurements, drastically enhances the Li + conductivity up to ≈1 mS cm −1 for Li 2.25 Zr 0.75 Fe 0.25 Cl 6. The superior interfacial stability when using Li 2+x Zr 1−x Fe x Cl 6 , as compared to that when using conventional Li 6 PS 5 Cl, is proved. Furthermore, an excellent electrochemical performance of the all-solid-state batteries is achieved via the combination of Li 2 ZrCl 6 and single-crystalline LiNi 0.88 Co 0.11 Al 0.01 O 2 .

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New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe³⁺‐Substituted Li₂ZrCl₆

Kwak

Han

Lyoo

et al. 2021

Advanced Energy Materials

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177

188

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“…[21,22] Although Arsenic (As)substituted Li 4 SnS 4 SSEs can increase the ionic conductivity to 10 −3 S cm −1 at RT, the hyper toxic As-based compounds prevent their commercialization. [22] Very recently, fractional substitution of P with Sn, Sb, or Zn in the crystallized sulfide SSEs have been reported to improve the air-stability, [23][24][25][26] but either insufficient ionic conductivity or poor compatibility with Li metal has impeded them to be used as a single-layer electrolyte for applications. To improve the Li metal compatibility, in addition to the additional and complicated interfacial modification (i.e., pre-treatment of Li metal and utilization of interlayers), [27][28][29][30] synthesizing sulfide SSEs with introducing halide elements has been verified as a more effective strategy that can increase the exchange current density and reduce the manufacturing cost.…”

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An Air‐Stable and Li‐Metal‐Compatible Glass‐Ceramic Electrolyte enabling High‐Performance All‐Solid‐State Li Metal Batteries

et al. 2021

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All-solid-state lithium metal batteries (ASSLMBs) have been regarded as ideal energy storage devices because of their potential to maximize energy density and improve safety. [1-3] As a key part of ASS-LMBs, the development of solid-state electrolytes (SSEs) has drawn increasing attention. [4,5] Among the various types of SSEs, the inorganic glass-ceramic SSE is one of the most promising categories. [6,7] Apart from the advantages of high ionic conductivity and superior mechanical properties in comparison to organic polymer-based SSEs, the glass-ceramic SSEs also show minimal grain boundary resistance and good contact with electrode materials compared to other inorganic ceramic SSEs. [8,9] Sulfide-based glass-ceramic SSEs have received great attention due to their relatively low glass transition temperature (T g , lower than 300 °C). [6,10] The metastable Li-ion conductors (e.g., β-Li 3 PS 4 and Li 7 P 3 S 11) can be precipitated from glass precursors and stabilized in a glass The development of all-solid-state Li metal batteries (ASSLMBs) has attracted significant attention due to their potential to maximize energy density and improved safety compared to the conventional liquid-electrolyte-based Li-ion batteries. However, it is very challenging to fabricate an ideal solid-state electrolyte (SSE) that simultaneously possesses high ionic conductivity, excellent air-stability, and good Li metal compatibility. Herein, a new glassceramic Li 3.2 P 0.8 Sn 0.2 S 4 (gc-Li 3.2 P 0.8 Sn 0.2 S 4) SSE is synthesized to satisfy the aforementioned requirements, enabling high-performance ASSLMBs at room temperature (RT). Compared with the conventional Li 3 PS 4 glass-ceramics, the present gc-Li 3.2 P 0.8 Sn 0.2 S 4 SSE with 12% amorphous content has an enlarged unit cell and a high Li + ion concentration, which leads to 6.2-times higher ionic conductivity (1.21 × 10 −3 S cm −1 at RT) after a simple cold sintering process. The (P/Sn)S 4 tetrahedron inside the gc-Li 3.2 P 0.8 Sn 0.2 S 4 SSE is verified to show a strong resistance toward reaction with H 2 O in 5%-humidity air, demonstrating excellent air-stability. Moreover, the gc-Li 3.2 P 0.8 Sn 0.2 S 4 SSE triggers the formation of Li-Sn alloys at the Li/SSE interface, serving as an essential component to stabilize the interface and deliver good electrochemical performance in both symmetric and full cells. The discovery of this gc-Li 3.2 P 0.8 Sn 0.2 S 4 superionic conductor enriches the choice of advanced SSEs and accelerates the commercialization of ASSLMBs.

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“…To address the demand, there have been various synthesis methods developed to produce MMOs with intended properties. The ceramic method, in which two or more metal oxide components are mixed and thermally treated, is the most common method [11,12]; however, it takes high energy to facilitate diffusion of metal species between different lattice structures. The sol-gel process, which consists of conversion of monomer to colloid (sol) and further aging to integrated network (gel), is another method to prepare MMO [13][14][15].…”

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Development of Mesopore Structure of Mixed Metal Oxide through Albumin-Templated Coprecipitation and Reconstruction of Layered Double Hydroxide

Jung

Kim

2021

Nanomaterials

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Mixed metal oxide (MMO) with relatively homogeneous mesopores was successfully obtained by calcination and reconstruction of albumin-templated layered double hydroxide (LDH). The aggregation degree of albumin-template was controlled by adjusting two different synthesis routes, coprecipitation and reconstruction. X-ray diffraction patterns and scanning electron microscopic images indicated that crystal growth of LDH was fairly limited during albumin-templated coprecipitation due to the aggregation. On the hand, crystal growth along the lateral direction was facilitated in albumin-templated reconstruction due to the homogeneous distribution of proteins moiety. Different state of albumin during LDH synthesis influenced the local disorder and porous structure of calcination product, MMO. The N2 adsorption-desorption isotherms demonstrated that calcination on reconstructed LDH produced MMO with large specific surface area and narrow distribution of mesopores compared with calcination of coprecipitated LDH.

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Li+ conduction in air-stable Sb-Substituted Li4SnS4 for all-solid-state Li-Ion batteries

Cited by 86 publications

References 55 publications

New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe³⁺‐Substituted Li₂ZrCl₆

New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe³⁺‐Substituted Li₂ZrCl₆

An Air‐Stable and Li‐Metal‐Compatible Glass‐Ceramic Electrolyte enabling High‐Performance All‐Solid‐State Li Metal Batteries

Development of Mesopore Structure of Mixed Metal Oxide through Albumin-Templated Coprecipitation and Reconstruction of Layered Double Hydroxide

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Li+ conduction in air-stable Sb-Substituted Li4SnS4 for all-solid-state Li-Ion batteries

Cited by 86 publications

References 55 publications

New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe3+‐Substituted Li2ZrCl6

New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe3+‐Substituted Li2ZrCl6

An Air‐Stable and Li‐Metal‐Compatible Glass‐Ceramic Electrolyte enabling High‐Performance All‐Solid‐State Li Metal Batteries

Development of Mesopore Structure of Mixed Metal Oxide through Albumin-Templated Coprecipitation and Reconstruction of Layered Double Hydroxide

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New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe³⁺‐Substituted Li₂ZrCl₆

New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe³⁺‐Substituted Li₂ZrCl₆