Degradation of an argyrodite-type sulfide solid electrolyte by a trace of water: A spectroscopic analysis

Morino, Yonezo; Sano, Hikaru; Kawamoto, Koji; Fukui, Kiichi; Takeuchi, Masato; Sakuda, Atsushi; Sakuda, Atsushi

doi:10.1016/j.ssi.2023.116162

Cited by 20 publications

(66 citation statements)

References 41 publications

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“…1 shows the electrochemical impedance spectroscopy (EIS) results before and after exposure to air containing a small amount of water. As already reported, 19,20,[23][24][25][26][27][28][29] the lithium ionic 115 conductivity drastically deteriorated upon exposure from 1.7 × 10 −3 to 5.3 × 10 −4 S cm −1 (the conductivity retention was ~31%) because of the presence of surface decomposed compounds and adsorbed water molecules. 19,20 Next, we investigated the performance of the positive electrode half-cells using unexposed-SE and exposed-SE.…”

Section: Resultssupporting

confidence: 53%

“…The sample preparation and cell fabrication were conducted as described in our previous reports. 2,10,11,19,20 Briefly, an argyrodite-structured Li7-xPS6-xClx (x ~ 1, D50 = 0.7 µm, Mitsui Mining and Smelting) was used as the sulfide-based SE. The SE powder was exposed to air with a d. p. of −20°C at a flow rate of 0.8 L min −1 for 1 h to prepare a moisture-exposed sample (hereinafter referred 80 to as exposed-SE.…”

Section: Methodsmentioning

confidence: 99%

“…p. 19,20 The lithium ionic conductivity was measured by pressing SE at 98-588 MPa and sandwiching it between carbon-coated Al foil electrodes at about 100 MPa. LiNbO3-coated LiNi0.5Co0.2Mn0.3O2 85 (NCM523, Sumitomo Metal Mining) was used as the positive electrode active material.…”

Section: Methodsmentioning

confidence: 99%

“…Therefore, to gain more insight into the moisture-induced SE degradation in actual battery manufacturing processes, we 65 previously investigated the influence of a small amount of water under dry-room-simulated conditions ACCEPTED MANUSCRIPT 5 with a dew point (d. p.) of −20°C, which are closer to actual battery manufacturing environment. 19,20 The exposure to controlled low-moisture air revealed a sequential degradation mechanism involving H2S gas generation, 19 increase in the electrochemical impedance, 19 and growth of surface decomposition compounds and adsorbed water molecules. 20 70 However, despite these advances, the influence of the exposure to moisture on the ASSB cell performance remains unclear.…”

Section: Introductionmentioning

confidence: 99%

“…19,20 The exposure to controlled low-moisture air revealed a sequential degradation mechanism involving H2S gas generation, 19 increase in the electrochemical impedance, 19 and growth of surface decomposition compounds and adsorbed water molecules. 20 70 However, despite these advances, the influence of the exposure to moisture on the ASSB cell performance remains unclear. In this study, we investigated the influence on the durability of an ASSB positive electrode with sulfide SE exposed to dry-room-simulated air containing a small amount of water.…”

Section: Introductionmentioning

confidence: 99%

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Positive Electrode Performance of All-Solid-State Battery with Sulfide Solid Electrolyte Exposed to Low-Moisture Air

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Section: Resultssupporting

confidence: 53%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Critical Factors Contributing to the Thermal Runaway of Thiophosphate Solid Electrolytes for All‐Solid‐State Batteries

Kim,

Chang,

Song

et al. 2024

Adv Funct Materials

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Although all‐solid‐state batteries are suggested as a means to tackle the safety concerns associated with current Li‐ion batteries, there is presently a lack of comprehensive understanding regarding their thermal safety. In this context, critical factors contributing to the thermal runaway of thiophosphate solid electrolytes with charged Li1‐xNi0.8Co0.1Mn0.1O2 (NCM) under thermal and mechanical abuse conditions are demonstrated, considering parameters such as heating rate under thermal abuse conditions and the hybridization of S atom in structure. In particular, the thermal behavior of various solid electrolytes, including thiophosphates, thioantimonates, and halides, is investigated to clarify critical elements in Li6PS5Cl (LPSCl) contributing to its thermal instability when combined with charged NCM. Various ex situ analyses, along with density functional theory calculations, reveal a correlation between the hybridization of S atoms and the thermal instability of solid electrolytes, suggesting that sulfur acts as a key element triggering the thermal runaway of sulfide‐based solid electrolytes.

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Ultrathin Superhydrophobic Coatings for Air‐Stable Inorganic Solid Electrolytes: Toward Dry Room Application for All‐Solid‐State Batteries

Kim,

Woo,

Kim

et al. 2023

Advanced Energy Materials

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Inorganic solid electrolytes (SEs), such as sulfides and halides, are crucial for developing practical all‐solid‐state batteries (ASSBs) owing to their high ionic conductivities and mechanical sinterabilities. However, their sensitivity to humid air necessitates stringent dry‐room conditions during processing, which increases production costs. This study demonstrates that ultrathin (≈5 nm) superhydrophobic polydimethylsiloxane (PDMS) or fluorinated PDMS (F‐PDMS) protective layers can enhance the stability of air‐sensitive sulfide (Li6PS5Cl (LPSCl)) and halide (Li2.5Zr0.5In0.5Cl6) SEs in ASSBs. The (F)‐PDMS coatings are applied using a scalable, straightforward vapor‐phase deposition process, achieving high Li+ conductivity retention (92%, from 2.5 to 2.3 mS cm−1 at 30 °C). The protective layers effectively inhibit LPSCl degradation under practically relevant dry room conditions (dew point of −50 °C or −10 °C): e.g., from 2.3 to 0.97 mS cm−1 for PDMS‐coated LPSCl versus from 2.5 to 0.57 mS cm−1 for bare LPSCl. Surprisingly, the superhydrophobic coatings facilitate the recovery of Li+ conductivity via vacuum heat treatment. This new phenomenon, known as regeneration, is achieved by the facile elimination of adsorbed water. Furthermore, the regenerated (F)‐PDMS‐coated LPSCl demonstrates significant performance in NCM||Li‐In ASSB cells. These findings suggest that superhydrophobic (F)‐PDMS coatings are a promising solution for practical all‐solid‐state technologies.

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Degradation of an argyrodite-type sulfide solid electrolyte by a trace of water: A spectroscopic analysis

Cited by 20 publications

References 41 publications

Positive Electrode Performance of All-Solid-State Battery with Sulfide Solid Electrolyte Exposed to Low-Moisture Air

Positive Electrode Performance of All-Solid-State Battery with Sulfide Solid Electrolyte Exposed to Low-Moisture Air

Critical Factors Contributing to the Thermal Runaway of Thiophosphate Solid Electrolytes for All‐Solid‐State Batteries

Ultrathin Superhydrophobic Coatings for Air‐Stable Inorganic Solid Electrolytes: Toward Dry Room Application for All‐Solid‐State Batteries

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