Synthesis of sulfide solid electrolytes from Li2S and P2S5 in anisole

Maniwa, Riku; Calpa, Marcela; Rosero-Navarro, Nataly Carolina; Miura, Akira; Tadanaga, Kiyoharu

doi:10.1039/d0ta08658d

Cited by 25 publications

(29 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ionic conductivity varies by one order of magnitude, even when the manufacturing conditions are only slightly different. [10,12,13,20,[41][42][43][44] This fact indicates that the conventional methods involve difficulty in achieving intrinsic high conductivity for Li 7 P 3 S 11 during large-scale manufacturing. Our solution processing technology dramatically reduces the processing time for the wet-chemical reaction from 24 to 72 h in conventional liquid-phase synthesis to %2 min, leading to improved producibility, cost, scalability, and performance compared to the SEs produced by conventional methods.…”

Section: Structural and Electrochemical Propertiesmentioning

confidence: 99%

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

Gamo

Nishida

Nagai

et al. 2022

Adv Energy and Sustain Res

View full text Add to dashboard Cite

Solution processing technology for the manufacturing of all‐solid‐state batteries (ASSBs) holds great promise of scalability and low cost over ball milling and solid‐state methods. However, conventional liquid‐phase synthesis for solid electrolytes has yet to translate into large‐scale manufacturing to address commercialization challenges. Herein, solution processing via dynamic sulfide radical anions is developed, providing rapid and scalable manufacturing of Li7P3S11 solid electrolytes (SEs). A mixture of Li2S, P2S5, and excess elemental sulfur in a mixed solvent of acetonitrile, tetrahydrofuran, and ethanol forms a homogenous precursor solution containing the S3 ·− radical anion. The presence of ethanol enhances the chemical stability of S3 ·−. The resulting sulfide radical anions serve as a mediator with two strategies: the soluble polysulfide formation and activation of P2S5, and thus allows the generation of the precursor solution in 2 min. The Li7P3S11 is prepared in 2 h without the need for ball milling or high‐energy treatment, which shows higher ionic conductivity (1.2 mS cm−1 at 25 °C) and excellent cell performance of ASSBs cells than Li7P3S11 prepared by ball milling. The solution processing technology reported here paves the way for the accelerated adoption of practical ASSBs manufacturing.

show abstract

Section: Structural and Electrochemical Propertiesmentioning

confidence: 99%

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

Gamo

Nishida

Nagai

et al. 2022

Adv Energy and Sustain Res

View full text Add to dashboard Cite

show abstract

“…18,27−30,34−36,39,44,45,63−69 The ionic conductivity of Li 6 PS 5 Cl electrolytes made via solid-phase methods scattered in the range of 1−10 mS/cm, where the higher values seemed mainly from hot-pressing or fast-sintering treatments during the pellet fabrications. 29,44 The liquid-phase methods could also make Li 6 PS 5 Cl electrolytes with the ionic conductivity around 2 mS/cm, 18,30,34,36 including ours herein (Figure 12a). Regarding the cyclability, our electrolyte presented the second best performance with 400 cycles at 1 C, leaving far behind the third best with 250 cycles at 1 / 10 C 39 and all others below 100 cycles (Figure 12b).…”

Section: Resultsmentioning

confidence: 71%

“…The ionic conductivity of Li 6 PS 5 Cl electrolytes produced via solution methods has been remarkably improved from 10 −2 mS/cm in 2015 33 to above 2 mS/cm in 2019, 18,34 getting comparable with the solid-state methods. 27,35 However, the long-term cyclability of Li 6 PS 5 Cl electrolytes by liquid-phase methods were barely reported.…”

Section: Introductionmentioning

confidence: 99%

A Low-Cost Liquid-Phase Method of Synthesizing High-Performance Li₆PS₅Cl Solid-Electrolyte

Han

Tian

Fang

et al. 2022

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Li 6 PS 5 Cl is an extensively studied sulfide-solidelectrolyte for developing all-solid-state lithium batteries. However, its practical application is hindered by the high cost of its raw material lithium sulfide (Li 2 S), the difficulty in its massive production, and its substandard performance. Herein we report an economically viable and scalable method, denoted as "de novo liquid phase method", which enables in synthesizing highperformance Li 6 PS 5 Cl without using commercial Li 2 S but instead in situ making Li 2 S from cheap materials of lithium chloride (LiCl) and sodium sulfide. LiCl, a raw material needed for making both Li 2 S and Li 6 PS 5 Cl, can be added at a full-scale in the beginning and unrequired to separate when making the intermediate Li 3 PS 4 . Such a consecutive feature makes this method time-efficient; and the excess amount of LiCl in the step of making Li 2 S also facilitates removing the byproduct of sodium chloride via the common ion effect. The materials cost of this method for Li 6 PS 5 Cl is ∼ $55/kg, comparable with the practical need of $50/kg. Moreover, the obtained Li 6 PS 5 Cl shows high ionic conductivity and outstanding cyclability in full battery tests, that is, ∼2 mS/cm and >99.8% retention for 400+ cycles at 1 C, respectively. Thus, this innovative method is expected to pave the way to develop practical sulfide-solid-electrolytes for all-solid-state lithium batteries.

show abstract

“…In 2012, Li 7 P 3 S 11 was synthesized as a high lithium-ion conductor in dimethyl ether (DME) solvent with a maximum ionic conductivity of 2.7 × 10 –4 S cm –1 at room temperature 15 . Following this, Li 7 P 3 S 11 was prepared using ACN, THF, and anisole solvents; the highest ionic conductivity was achieved using ACN solvent 16 , 17 . A wet chemical reaction mechanism for the formation of Li 7 P 3 S 11 phase in ACN has also been proposed.…”

Section: Introductionmentioning

confidence: 99%

The effect of solvent on reactivity of the Li2S–P2S5 system in liquid-phase synthesis of Li7P3S11 solid electrolyte

Gamo

Nagai

Matsuda

2021

Sci Rep

View full text Add to dashboard Cite

Synthesis technology for sulfide-based solid electrolytes based on liquid-phase processing has attracted significant interest in relation to achieving the optimal design for all-solid-state batteries. Herein, guidelines to solvent selection for the liquid-phase synthesis of superionic conductor Li7P3S11 are described through systematic examination. 70Li2S–30P2S5 system, a source of Li7P3S11, is treated via a wet chemical reaction using eight organic solvents with different physical and chemical properties (i.e., dielectric constant, molecule structure, and boiling point). We reveal that the solvent’s polarity, characterized by the dielectric constant, plays an important role in the formation of crystalline Li7P3S11 via wet chemical reaction. In addition, acetonitrile (ACN) solvent with a high dielectric constant was found to lead to high-purity crystalline Li7P3S11 and intrinsically high ionic conductivity. Further, solvents with a high boiling point and ring structures that cause steric hindrance were found to be unfavorable for the wet chemical synthesis of Li7P3S11 solid electrolyte. Overall, we demonstrate that ACN solvent is the most suitable for the liquid-phase synthesis of a crystalline Li7P3S11 solid electrolyte with high purity based on its dielectric constant, molecular structure, and boiling point.

show abstract

Synthesis of sulfide solid electrolytes from Li₂S and P₂S₅ in anisole

Abstract: We report the liquid-phase synthesis of sulfide solid electrolytes from Li2S and P2S5 using anisole at 200–300 °C under microwave irradiation, in which β-Li3PS4 and Li7P3S11 were directly precipitated in anisole in 30 min.

Cited by 25 publications

References 40 publications

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

A Low-Cost Liquid-Phase Method of Synthesizing High-Performance Li₆PS₅Cl Solid-Electrolyte

The effect of solvent on reactivity of the Li2S–P2S5 system in liquid-phase synthesis of Li7P3S11 solid electrolyte

Contact Info

Product

Resources

About

Synthesis of sulfide solid electrolytes from Li2S and P2S5 in anisole

Abstract: We report the liquid-phase synthesis of sulfide solid electrolytes from Li2S and P2S5 using anisole at 200–300 °C under microwave irradiation, in which β-Li3PS4 and Li7P3S11 were directly precipitated in anisole in 30 min.

Cited by 25 publications

References 40 publications

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

A Low-Cost Liquid-Phase Method of Synthesizing High-Performance Li6PS5Cl Solid-Electrolyte

The effect of solvent on reactivity of the Li2S–P2S5 system in liquid-phase synthesis of Li7P3S11 solid electrolyte

Contact Info

Product

Resources

About

Synthesis of sulfide solid electrolytes from Li₂S and P₂S₅ in anisole

A Low-Cost Liquid-Phase Method of Synthesizing High-Performance Li₆PS₅Cl Solid-Electrolyte