Determination of thermodynamic properties of Na2S using solid-state EMF measurements

Lindberg, Gustav; Larsson, Anders; Råberg, Mathias; Boström, Dan; Backman, Rainer; Nordin, Anders

doi:10.1016/j.jct.2006.06.003

Cited by 11 publications

(3 citation statements)

References 5 publications

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“…The temperature on the Li/Na side of the ampoule was kept at the same or higher value than the temperature on the S side in order to avoid the condensation of S vapor. The expected solid–vapor chemical reaction is as follows 48 , 49 In contrast to the fact that Li 2 S is the only thermodynamically stable phase in the Li–S system, 50 the possibility of formation of sodium polysulfides such as Na 2 S 2 , Na 2 S 4 , and Na 2 S 5 cannot be excluded in the Na case. 51 …”

Section: Resultsmentioning

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: Resultsmentioning

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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“…The salts employed are typically low cost and widely available. The first reaction of interest is the thermodynamically favorable metathesis reaction between Na 2 S and SbCl 3 : 36,37 [ ]…”

Section: Resultsmentioning

confidence: 99%

Solution Synthesis of Sb₂S₃ and Na₃SbS₄ Solid-State Electrolyte

Vaselabadi¹,

Smith²,

Wolden³

2021

J. Electrochem. Soc.

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Sodium thioantimonate (Na3SbS4) is an attractive solid-state electrolyte for sodium-ion batteries due to its high ionic conductivity and stability in protic solvents. Herein, we describe solution-based routes for its synthesis. First, we demonstrate the synthesis of the Sb2S3 precursor via thermodynamically favorable metathesis between Na2S and SbCl3. This solution-based approach is further extended to couple the resulting Sb2S3 with Na2S for the synthesis of Na3SbS4. It is shown that ethanol is a superior solvent to water for solution-based synthesis of Na3SbS4 with respect to yield, morphology, and performance. Amorphous Sb2S3 synthesized from low-temperature metathesis produced highly crystalline Na3SbS4 with a room temperature Na+ conductivity of 0.52 mS cm−1 and low activation energy, comparable to leading values reported in the literature.

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“…The appearance of a miniscule concentration (0.07-0.11% w/w) of Na 2 CO 3 in the product (not clearly visible in Fig. 2) might be due to the reaction between the atmospheric CO 2 and NaOH during the preparation of NaOH solution (Gondolfe and Kurukchi 1997; Bagreev and Bandosw 2002) and due to the reaction between Na 2 S in the product and atmospheric CO 2 during titration (Lindberg et al 2007).…”

Section: Effect Of H 2 S Flow Ratementioning

confidence: 99%

Optimization of Sodium Hydrosulfide Synthesis for Metal Recovery from Wastewater Using Flue Gas Containing H2S

Kim

Behera²,

Jamal

et al. 2016

J. Environ. Eng.

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Sodium hydrosulfide (NaSH), which is utilized for recovering rare metals, was synthesized in a laboratory-scale batch reactor by absorbing a simulated flue gas containing H 2 S into NaOH solution. The effects of H 2 S flow rate, NaOH concentration, and reaction time on the synthesis of NaSH were examined. With an increase in the H 2 S flow rate, the absorption ratio, conversion ratio, and total NaSH productivity showed a decreasing tendency. On the other hand, a higher concentration of NaSH could be synthesized with a higher concentration of NaOH. Most of the Na 2 S (the intermediate product) were produced at a pH > 12, and the NaSH synthesis reaction was feasible at a pH 11.5. Contrary to the increased H 2 S flow rate, increased NaOH concentration resulted in an enhanced Na 2 S=NaSH ratio. With a maximum equivalent ratio of NaOH=H 2 S at 0.88, the chemical composition of the product could maintain equilibrium with the highest NaSH concentration and less than 1% weight-to-weight ratio (w/w) Na 2 S concentration.

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Determination of thermodynamic properties of Na2S using solid-state EMF measurements

Cited by 11 publications

References 5 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

Solution Synthesis of Sb₂S₃ and Na₃SbS₄ Solid-State Electrolyte

Optimization of Sodium Hydrosulfide Synthesis for Metal Recovery from Wastewater Using Flue Gas Containing H2S

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Determination of thermodynamic properties of Na2S using solid-state EMF measurements

Cited by 11 publications

References 5 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

Solution Synthesis of Sb2S3 and Na3SbS4 Solid-State Electrolyte

Optimization of Sodium Hydrosulfide Synthesis for Metal Recovery from Wastewater Using Flue Gas Containing H2S

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Solution Synthesis of Sb₂S₃ and Na₃SbS₄ Solid-State Electrolyte