Quantitative analysis of crystallinity in an argyrodite sulfide-based solid electrolyte synthesized <i>via</i> solution processing

Yubuchi, So; Tsukasaki, Hirofumi; Sakuda, Atsushi; Mori, Shigeo; Hayashi, Akitoshi; Tatsumisago, Masahiro

doi:10.1039/c9ra00949c

Cited by 23 publications

(27 citation statements)

References 46 publications

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“…Theh Oi st ypical of solid electrolytes and proton conductors,a nd is within the same range of our measured values. [41,42] We acknowledge,however, that our conductivities are in the lower range for Li + /Na + ,and are more in line with proton conductors,this being attributed to the disordered nature of these materials.T he electronic activation energy for both the hydrated and dehydrated phase are typical of MIEC and are comparable to literature values. [43,44] With the stable and reversible mixed cationic and anionic redox mechanism in < Na 2 MoS 4 > confirmed, we continued our analysis of the charge-storage performance in Li halfcells.S ince the electronic conductivity of < Na 2 MoS 4 > was higher than of several conventional inorganic materials (for example,L i 4 Ti 5 O 12 -1 0 À13 Scm À1 ,L iFePO 4 -1 0 À9 Scm À1 , or LiMn 2 O 4 -1 0 À6 Scm À1 ) [45] we assembled and cycled < Na 2 MoS 4 > electrodes with no conductive carbon additives.…”

Section: Methodsmentioning

confidence: 73%

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

et al. 2020

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We report the electrochemistry of a hitherto unexplored Na2MoS4 phase as a conversion electrode material for Na‐ and Li‐ion batteries. The material adopts an amorphous coordination polymer structure with mixed Mo and S valences. XPS and XRD analysis reveal a complex interplay between Mo and S redox chemistry, while excluding the formation of free sulfur, lithium sulfide, or other crystalline phases. Na2MoS4 behaves as a mixed ionic–electronic conductor, with electronic conductivity of 6.1×10−4 S cm−1, that permits carbon‐free application in an electrochemical cell. A reversible capacity of up to 500 mAh g−1 was attained, corresponding to a five‐electron redox exchange, with species ranging from (highest oxidized state) to 5MoS4> (lowest oxidized state). This study emphasizes the excellent charge‐storage performances of Na2MoS4 for Li‐ or Na‐ion batteries, and enriches the emerging library and knowledge of sulfide phases with mixed anionic and cationic redox properties.

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Section: Methodsmentioning

confidence: 73%

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

et al. 2020

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“…Low-crystalline SE materials including such solution-processed Li-argyrodites and mechanical-milling-derived samples (e.g., glasses and glass-ceramics) are important for ASLBs. ,− It was suggested that inconsistencies in the reported values of Li + conductivities for Li–P–S glass-ceramics (e.g., Li 3 PS 4 ) were associated with complex local phase evolution, which varied with synthesis conditions and precursors . Transmission electron microscopy (TEM) analysis could be a straightforward method for disclosing the microstructures of such low crystalline materials.…”

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confidence: 99%

“…The contrasting behavior of Li + conductivities for sol-LPGeSI and sol-LPSI upon varying the heat-treatment temperature could be understood by considering their microstructural evolution as follows. Solution-processed SEs heat-treated at a low temperature of 180 °C would have glass-ceramic structures in which nanocrystalline and amorphous phases coexist. ,,, As illustrated in Figure e, the crystalline phase would grow as the heat-treatment temperature is increased, which is beneficial for LPGeSI but detrimental for LPSI. Thus, distinctly opposite contributions of highly crystalline LPGeSI and LPSI phases, respectively, could be responsible for the overall behavior of Li + conductivities for solution-processed Li argyrodites.…”

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confidence: 99%

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Tailoring Solution-Processable Li Argyrodites Li_6+xP_1–xM_xS₅I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries

et al. 2020

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Owing to their high Li + conductivities, mechanical sinterability, and solution processability, sulfide Li argyrodites have attracted much attention as enablers in the development of highperformance all-solid-state batteries with practicability. However, solution-processable Li argyrodites have been developed only for a composition of Li 6 PS 5 X (X = Cl, Br, I) with insufficiently high Li + conductivities (∼10 −4 S cm −1 ). Herein, we report the highest Li + conductivity of 0.54 mS cm −1 at 30 °C (Li 6.5 P 0.5 Ge 0.5 S 5 I) for solution-processable iodine-based Li argyrodites. A comparative investigation of three iodine-based argyrodites of unsubstituted and Ge-and Sn-substituted solution-processed Li 6 PS 5 I with varied heat-treatment temperature elucidates the effect of microstructural evolution on Li + conductivity. Notably, local nanostructures consisting of argyrodite nanocrystallites in solution-processed Li 6.5 P 0.5 Ge 0.5 S 5 I have been directly captured by cryogenic transmission electron microscopy, which is a first for sulfide solid electrolyte materials. Specifically, the promising electrochemical performances of all-solid-state batteries at 30 °C employing LiCoO 2 electrodes tailored by the infiltration of Li 6.5 P 0.5 Ge 0.5 S 5 I−ethanol solutions are successfully demonstrated.

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“…Figure 9 shows the synthesis procedure of lithium argyrodite electrolyte with high conductivity via a simple solution process using THF and EtOH dual solvents. [64] The reaction in the liquid phase is shown in Equation (5).…”

Section: Wet-chemical Methodsmentioning

confidence: 99%

Designing Lithium Argyrodite Solid‐State Electrolytes for High‐Performance All‐Solid‐State Lithium Batteries

Zhang

Miao

et al. 2021

Batteries & Supercaps

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All‐solid‐state lithium batteries (ASSLBs) with desirable advantages, such as high safety and energy density, simple packaging, and wide temperature tolerance, are considered promising energy storage devices to replace traditional lithium‐ion batteries with organic liquid electrolytes. Solid‐state electrolytes (SSEs) are the critical component in ASSLBs. Argyrodites, as a typical class of sulfide‐based lithium‐ion superconductors, represent the most promising SSEs with respect to their high ionic conductivity at room temperature, low cost, good compatibility towards Li metal, and extraordinary performance reported in ASSLBs. However, lithium argyrodites are inert gas‐protective, moisture‐sensitive, interface‐unstable, and working potential window‐limited, presenting the main challenges for their commercial use. In this review, we comprehensively summarized the basic physical and chemical properties, material synthesized strategies, chemical or electrochemical stabilities, and interface engineering of lithium argyrodite SSEs. Furthermore, the recent achievements and critical challenges for lithium argyrodite from the material level to battery applications are overviewed, and the future development opportunities of integrating the lithium argyrodite SSEs into ASSLBs have been prospected.

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Quantitative analysis of crystallinity in an argyrodite sulfide-based solid electrolyte synthesized via solution processing

Abstract: Liquid-phase synthesis is a useful technique for preparing argyrodite sulfide-based solid electrolytes, and the synthesis conditions such as heat treatment strongly affect the conductivity.

Cited by 23 publications

References 46 publications

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

Tailoring Solution-Processable Li Argyrodites Li_6+xP_1–xM_xS₅I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries

Designing Lithium Argyrodite Solid‐State Electrolytes for High‐Performance All‐Solid‐State Lithium Batteries

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Quantitative analysis of crystallinity in an argyrodite sulfide-based solid electrolyte synthesized via solution processing

Abstract: Liquid-phase synthesis is a useful technique for preparing argyrodite sulfide-based solid electrolytes, and the synthesis conditions such as heat treatment strongly affect the conductivity.

Cited by 23 publications

References 46 publications

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework

Tailoring Solution-Processable Li Argyrodites Li6+xP1–xMxS5I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries

Designing Lithium Argyrodite Solid‐State Electrolytes for High‐Performance All‐Solid‐State Lithium Batteries

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Tailoring Solution-Processable Li Argyrodites Li_6+xP_1–xM_xS₅I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries