Lithium ion conductivity in Li2S–P2S5 glasses – building units and local structure evolution during the crystallization of superionic conductors Li3PS4, Li7P3S11 and Li4P2S7

Dietrich, Christian; Weber, Dominik; Sedlmaier, Stefan J.; Indris, Sylvio; Culver, Sean P.; Walter, Dirk; Janek, Jürgen; Zeier, Wolfgang G.

doi:10.1039/c7ta06067j

Cited by 274 publications

(361 citation statements)

References 61 publications

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“…[ 36 ] The Raman spectra (Figure S6, Supporting Information) showed ortho ‐thiophosphate species (PS 4 3− ) as the dominant species at 421 ± 1 cm −1 , known to be responsible for the high ionic conductivity in Li thiophosphate glasses. [ 37 ] In addition, hypo ‐thiophosphate species (P 2 S 6 4− ) at around 380 cm −1 were detected, in agreement with Dietrich et al for this composition. [ 37 ] The intensity of both signals were independent from the densification conditions, therefore, the concentration of PS 4 3− and P 2 S 6 4− are believed to be the same among all samples.…”

Section: Resultssupporting

confidence: 88%

Correlating Macro and Atomic Structure with Elastic Properties and Ionic Transport of Glassy Li₂S‐P₂S₅ (LPS) Solid Electrolyte for Solid‐State Li Metal Batteries

Garcia‐Mendez

Smith

Neuefeind

et al. 2020

Advanced Energy Materials

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all-solid-state batteries (ASSBs). [1] ASSBs have garnered interest since they offer the potential for improved safety and energy density compared to lithium-ion batteries. To realize these advantages, the nonflammable solid electrolyte would replace the flammable liquid electrolyte and Li metal would replace carbon anodes to reduce cell volume and weight. [2] As a result, about 100% higher energy densities could be achieved compared to conventional Li-ion batteries. [3,4] Sulfide-based electrolytes with adequate ionic conductivity, low interfacial resistance against electrodes, and low processing cost make them one of the most promising inorganic solid electrolyte materials that could enable ASSBs. [5] However, despite the development of different compositions through different synthesis techniques in the Li 2 S-P 2 S 5 (LPS) family, [6][7][8][9][10] the successful transition to Li metal with relevant charging rates (≥3 mA cm −2 at room temperature) has not been realized. It has been reported that microstructural defects, such as grain boundaries and/or pores can play a role in determining the maximum charging rate (or critical current density, CCD) a solid electrolyte can withstand without Li penetration. [11,12] Thus, a glassy, dense microstructure may be preferred for ASSB applications. In previous work, [13] the densification behavior or LPS 75-25 was studied as a function of temperature (25-300 °C) at fixed pressure (47 MPa). It was determined that crystallization of the thio-LiSICON III analog phase occurred between 170 and 250 °C. Moreover, the relative density was more or less invariant of densification temperature (≈80% RD; calculated dividing the geometrical density by its theoretical density in the amorphous phase: 1.88 g cm −3 ). [14] While in our previous study, the maximum hot-pressing pressure (47 MPa) was limited by the mechanical integrity of the molding die, we recently developed capabilities to increase pressure to achieve 360 MPa. With this new capability, the current study compliments our previous study by investigating the densification behavior of LPS 75-25 as a function of pressure at fixed temperature. The pressure ranged between 47 and 360 MPa and the temperature was fixed at the glass transition temperature (T glass ). We hypothesize that by increasing the molding pressure the relative density will increase. Furthermore, the simultaneous application of A combination of high ionic conductivity and facile processing suggest that sulfide-based materials are promising solid electrolytes that have the potential to enable Li metal batteries. Although the Li 2 S-P 2 S 5 (LPS) family of compounds exhibit desirable characteristics, it is known that Li metal preferentially propagates through microstructural defects, such as particle boundaries and/ or pores. Herein, it is demonstrated that a near theoretical density (98% relative density) LPS 75-25 glassy electrolyte exhibiting high ionic conductivity can be achieved by optimizing the molding pressure and temperature. The optimal molding pressur...

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Section: Resultssupporting

confidence: 88%

Correlating Macro and Atomic Structure with Elastic Properties and Ionic Transport of Glassy Li₂S‐P₂S₅ (LPS) Solid Electrolyte for Solid‐State Li Metal Batteries

Garcia‐Mendez

Smith

Neuefeind

et al. 2020

Advanced Energy Materials

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“…It is mainly constructed by the unit

{PS}_{4}^{3 -}

. However, by carefully checking the Raman spectrum of the intermediate in Figure , it is revealed that a large amount of

{normalP}_{2} {normalS}_{7}^{4 -}

exists, which typically appears in the Li 2 S‐P 2 S 5 system with Li 2 S content <70 mol% . Therefore, an amorphous phase with low Li 2 S content should also exist in the intermediate in our study, and it will react with the thio‐LISICON III analogous phase to form Li 7 P 3 S 11 .…”

Section: Resultsmentioning

confidence: 73%

“…As for the samples prepared in ACN, the major Raman signal around 400 cm −1 is composed of three bands. In the 230°C‐heat‐treated sample, the three bands locating at 392 cm −1 , 406 cm −1 , and 423 cm −1 can be assigned to hypo‐thiodiphosphate (

{normalP}_{2} {normalS}_{6}^{4 -}

), pyro‐thiophosphate (

{normalP}_{2} {normalS}_{7}^{4 -}

) and ortho‐thiophosphate (

{PS}_{4}^{3 -}

), respectively . These bands shift to high wave number in the precursor obtained after 180°C drying, especially the band attributed to

{PS}_{4}^{3 -}

, which shifts evidently from 423 cm −1 to 433 cm −1 due to the coordination of ACN molecules.…”

Section: Resultsmentioning

confidence: 98%

Solvent‐assisted ball milling for synthesizing solid electrolyte Li₇P₃S₁₁

Bai

Fan

et al. 2018

J Am Ceram Soc

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Solvent‐assisted ball milling is used to prepare the sulfide solid electrolyte Li7P3S11. Comparing with dry ball milling and simple liquid phase synthesis, solvent‐assisted ball milling can significantly promote the reaction of the starting materials from tens of hours to only several hours. When using dimethoxyethane as the assistant solvent, relatively pure Li7P3S11 with ionic conductivity of 1.0 × 10−4 S/cm can be synthesized after 8‐hour ball milling with following 2‐hour 180°C vacuum drying and 4‐hour 230°C heat treatment. It is revealed that the transition from the precursor to Li7P3S11 is a two‐step process, with an intermediate composed of a thio‐LISICON III analogous phase and an amorphous phase. This work not only provides a synthesis route of Li7P3S11 which reduces synthesis duration, but also offers an instructive insight into the phase evolution in solvent‐based synthesis process of sulfide solid electrolytes.

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“…Generally speaking, oxide‐based glasses exhibit rather low conductivity but better stability, whereas principally only sulfide‐based amorphous materials have achieved conductivities greater than 10 −3 S cm −1 , allowing them to be used in bulk‐type cells. Nonannealed glassy Li 2 S‐P 2 S 5 and Li 2 S‐P 2 S 5 ‐LiI exhibit conductivities of 2.8 × 10 −4 and 5.6 × 10 −4 S cm −1 , respectively, while 10 −3 S cm −1 is generally considered a benchmark for practical thick‐electrode cells . While sulfide glasses exhibit favorable mechanical properties and enable easy low‐temperature processability, they suffer from moisture stability .…”

Section: Introductionmentioning

confidence: 99%

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

Kaup

Bazak

Vajargah

et al. 2020

Advanced Energy Materials

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As potential next‐generation energy storage devices, solid‐state lithium batteries require highly functional solid state electrolytes. Recent research is primarily focused on crystalline materials, while amorphous materials offer advantages by eliminating problematic grain boundaries that can limit ion transport and trigger dendritic growth at the Li anode. However, simultaneously achieving high conductivity and stability in glasses is a challenge. New quaternary superionic lithium oxythioborate glasses are reported that exhibit high ion conductivity up to 2 mS cm−1 despite relatively high oxygen: sulfur ratios of more than 1:2, that exhibit greatly reduced H2S evolution upon exposure to air compared to Li7P3S11. These monolithic glasses are prepared from vitreous melts without ball‐milling and exhibit no discernable XRD pattern. Solid‐state NMR studies elucidate the structural entities that comprise the local glass structure which dictates fast ion conduction. Stripping/plating onto lithium metal results in very low polarization at a current density of 0.1 mA cm−2 over repeated cycling. Evaluation of the optimal glass composition as an electrolyte in an all‐solid‐state battery shows it exhibits excellent cycling stability and maintains near theoretical capacity for over 130 cycles at room temperature with Coulombic efficiency close to 99.9%, opening up new avenues of exploration for these quaternary compositions.

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Lithium ion conductivity in Li₂S–P₂S₅ glasses – building units and local structure evolution during the crystallization of superionic conductors Li₃PS₄, Li₇P₃S₁₁ and Li₄P₂S₇

Abstract: The local structure phase diagram of (Li2S)x(P2S5)100−x thiophosphates derived from pair distribution function crystallization experiments.

Cited by 274 publications

References 61 publications

Correlating Macro and Atomic Structure with Elastic Properties and Ionic Transport of Glassy Li₂S‐P₂S₅ (LPS) Solid Electrolyte for Solid‐State Li Metal Batteries

Correlating Macro and Atomic Structure with Elastic Properties and Ionic Transport of Glassy Li₂S‐P₂S₅ (LPS) Solid Electrolyte for Solid‐State Li Metal Batteries

Solvent‐assisted ball milling for synthesizing solid electrolyte Li₇P₃S₁₁

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

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Lithium ion conductivity in Li2S–P2S5 glasses – building units and local structure evolution during the crystallization of superionic conductors Li3PS4, Li7P3S11 and Li4P2S7

Abstract: The local structure phase diagram of (Li2S)x(P2S5)100−x thiophosphates derived from pair distribution function crystallization experiments.

Cited by 274 publications

References 61 publications

Correlating Macro and Atomic Structure with Elastic Properties and Ionic Transport of Glassy Li2S‐P2S5 (LPS) Solid Electrolyte for Solid‐State Li Metal Batteries

Correlating Macro and Atomic Structure with Elastic Properties and Ionic Transport of Glassy Li2S‐P2S5 (LPS) Solid Electrolyte for Solid‐State Li Metal Batteries

Solvent‐assisted ball milling for synthesizing solid electrolyte Li7P3S11

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

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Product

Resources

About

Lithium ion conductivity in Li₂S–P₂S₅ glasses – building units and local structure evolution during the crystallization of superionic conductors Li₃PS₄, Li₇P₃S₁₁ and Li₄P₂S₇

Correlating Macro and Atomic Structure with Elastic Properties and Ionic Transport of Glassy Li₂S‐P₂S₅ (LPS) Solid Electrolyte for Solid‐State Li Metal Batteries

Correlating Macro and Atomic Structure with Elastic Properties and Ionic Transport of Glassy Li₂S‐P₂S₅ (LPS) Solid Electrolyte for Solid‐State Li Metal Batteries

Solvent‐assisted ball milling for synthesizing solid electrolyte Li₇P₃S₁₁