Importance of multimodal characterization and influence of residual Li2S impurity in amorphous Li3PS4 inorganic electrolytes

Mirmira, Priyadarshini; Jin, Zheng; Ma, Peiyuan; Amanchukwu, Chibueze V.

doi:10.1039/d1ta02754a

Cited by 19 publications

(20 citation statements)

References 78 publications

(173 reference statements)

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“…β-Li 3 PS 4 was synthesized via a solvent-mediated synthesis as reported in the literature. − Li 2 S (99.9%, Sigma-Aldrich) and P 2 S 5 (98+%, Acros Organics) were mixed in a 3:1 molar ratio and poured to tetrahydrofuran (Fischer Scientific, anhydrous, synthesis grade) with a volume ratio of 1:20. The mixture was stirred for 24 h at room temperature under an Ar atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and Solid Electrolytes in Li and Na Metal Batteries

Lim

Fenk

Küster

et al. 2022

ACS Appl. Mater. Interfaces

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Realization of all-solid-state batteries combined with metallic Li/Na is still hindered due to the unstable interface between the alkali metal and solid electrolytes, especially for highly promising thiophosphate materials. Artificial and uniform solid-electrolyte interphases (SEIs), serving as thin ion-conducting films, have been considered as a strategy to overcome the issues of such reactive interfaces. Here, we synthesized sulfide-based artificial SEIs (Li x S y and Na x S y ) on Li and Na by solid/gas reaction between the alkali metal and S vapor. The synthesized films are carefully characterized with various chemical/electrochemical techniques. We show that these artificial SEIs are not beneficial from an application point of view since they either contribute to additional resistances (Li) or do not prevent reactions at the alkali metal/electrolyte interface (Na). We show that Na x S y is more porous than Li x S y , supported by (i) its rough morphology observed by focused ion beam-scanning electron microscopy, (ii) the rapid decrease of R interface (interfacial resistance) in Na x S y -covered-Na symmetric cells with liquid electrolyte upon aging under open-circuit potential, and (iii) the increase of R interface in Na x S y -covered-Na solid-state symmetric cells with Na 3 PS 4 electrolyte. The porous SEI allows the penetration of liquid electrolyte or alkali metal creep through its pores, resulting in a continuous chemical reaction. Hence, porosity of SEIs in general should be carefully taken into account in the application of batteries containing both liquid electrolyte and solid electrolyte.

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Section: Methodsmentioning

confidence: 99%

Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and Solid Electrolytes in Li and Na Metal Batteries

Lim

Fenk

Küster

et al. 2022

ACS Appl. Mater. Interfaces

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“…Amorphous Li 3 PS 4 was synthesized by using a 3:1 mole ratio of Li 2 S (99%) and P 2 S 5 according to our previously published procedure. 9 A total of 2 g of precursors was weighed and then hand-milled in a mortar and pestle for ∼10 min. The sample was then placed inside the milling jar with 32 g of 5 mm ZrO 2 balls, and the sample and balls were mechanically stirred for about 5 min.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

“…Solid state electrolytes are a promising alternative to liquids, with conductivities that approach, and in some cases surpass, those of commercial carbonate electrolytes. , Additionally, solid electrolytes can be nonflammable and nonvolatile . Inorganic electrolytes have high room temperature conductivity, but the mechanical properties of these materials are poor. , They are brittle and prone to cracking, and their high Young’s modulus (typically >10 GPa) suggests that they are inflexible and have a low formability in response to the pressure and volume changes that occur during battery cycling. , To offset the poor mechanical properties of inorganics, hybrid inorganic–polymer electrolytes have been studied.…”

Section: Introductionmentioning

confidence: 99%

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Nonconductive Polymers Enable Higher Ionic Conductivities and Suppress Reactivity in Hybrid Sulfide–Polymer Solid State Electrolytes

Mirmira

Fuschi

Gillett

et al. 2022

ACS Appl. Energy Mater.

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Hybrid ceramic−polymer solid state electrolytes are promising candidates to enable energy-dense lithium metal batteries by leveraging inorganic high ionic conductivity and flexible polymer mechanical properties. However, studies of hybrid electrolytes using sulfide-type inorganics such as Li 3 PS 4 (LPS) have largely focused on combining the inorganic with commercial poly(ethylene oxide) (PEO). PEO has proven to be insufficient for use in hybrid systems because it reacts with LPS and provides a competing pathway for ion transport, therefore producing a hybrid with low conductivity. Our work shows that using nonconductive, nonpolar polyethylene (PE) in hybrid electrolytes with LPS eliminates both polymer and inorganic degradation and remarkably, exhibits higher conductivities than those containing PEO at different polymer and salt concentrations. Using tracerexchange NMR, we observe that the nonconductive nature of PE allows for ion transport through the inorganic whereas PEO provides a separate, competing pathway for lithium transport. Furthermore, compared to pure LPS, these hybrids enable longer term lithium cycling at 60 °C. Our work shows that the path to enabling conductive and stable sulfide hybrids for solid state lithium-metal batteries may be through the use of nonconductive, nonreactive polymers.

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“…It has been feasible for fragmentation of large particles, amorphization, and fabrication of composites with uniform distribution of specific elements. 46–48 It is thus likely that the BM process is suitable for the activation of natural pyrite and sulfidation of ZVI.FeS 2 + 8H 2 O → Fe 3+ + 2SO 4 2− + 16H + + 15e − …”

Section: Introductionmentioning

confidence: 99%

Interaction of pyrite with zerovalent iron with superior reductive abilityviaFe(ii) regeneration

Zhi

Jian

et al. 2022

Environ. Sci.: Nano

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Importance of multimodal characterization and influence of residual Li₂S impurity in amorphous Li₃PS₄ inorganic electrolytes

Abstract: Amorphous Li3PS4 (LPS) solid-state electrolytes are promising for energy-dense lithium metal batteries. LPS glasses, synthesized from a 3:1 mol ratio of Li2S and P2S5, have high ionic conductivity and can...

Cited by 19 publications

References 78 publications

Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and Solid Electrolytes in Li and Na Metal Batteries

Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and Solid Electrolytes in Li and Na Metal Batteries

Nonconductive Polymers Enable Higher Ionic Conductivities and Suppress Reactivity in Hybrid Sulfide–Polymer Solid State Electrolytes

Interaction of pyrite with zerovalent iron with superior reductive abilityviaFe(ii) regeneration

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