NaGaS<sub>2</sub>: An Elusive Layered Compound with Dynamic Water Absorption and Wide‐Ranging Ion‐Exchange Properties

Klepov, Vladislav V.; Berseneva, Anna A.; Pace, Kristen A.; Kocevski, Vancho; Sun, Mengqi; Qiu, Peng; Wang, Hui; Chen, Fanglin; Besmann, Theodore M.; Loye, Hans-Conrad zur

doi:10.1002/anie.202001203

Cited by 19 publications

(45 citation statements)

References 51 publications

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“…Compared with LIC‐0.1 h and LIC‐0.6 h, the FTIP curve of LIC‐8.1 h shows a splitting of the peaks, which might correspond to the signal of crystal water and adsorbed water respectively. [ 38–42 ] This is in good agreement with the observation of TG. These results suggest that once the sample is exposed, crystalline hydrate will quickly form, as the exposure time becomes longer, the material will absorb more surface water.…”

Section: Resultssupporting

confidence: 91%

Air Sensitivity and Degradation Evolution of Halide Solid State Electrolytes upon Exposure

Wang

Cui

et al. 2021

Adv Funct Materials

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Halide solid state electrolytes (SSEs) have attracted the attention of researchers as a new family of SSEs due to simple synthesis, high ionic conductivity, and good softness. However, until now, most of the reported works are focused on promotion of ionic conductivity, and little attention is paid to their air stability and degradation mechanism upon exposure. Herein, the degradation evolution of typical halide SSEs upon moisture is investigated in detail. It is found both Li 3 InCl 6 and Li 3 YCl 6 halide SSEs are easy to absorb water and deteriorate, and the air sensitivity is closely related to the contact area with air. In comparison, the water absorption rate of Li 3 InCl 6 is faster than that of Li 3 YCl 6 , while the amount of water absorption of Li 3 YCl 6 is larger than that of Li 3 InCl 6 , due to the higher solubility of InCl 3 compared to YCl 3 . Along with water absorption, Li 3 InCl 6 first forms a crystalline hydrate, then partially decomposes to InCl 3 and LiCl, and InCl 3 further hydrolyzes and produces acid which is corrosive; finally In 2 O 3 impurities are formed. Coating the surface of Li 3 InCl 6 with Al 2 O 3 can effectively improve the air stability. This work can help to understand the degradation mechanism of halide SSEs and provide guidance for the future design of new halide SSEs.

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Section: Resultssupporting

confidence: 91%

Air Sensitivity and Degradation Evolution of Halide Solid State Electrolytes upon Exposure

Wang

Cui

et al. 2021

Adv Funct Materials

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“…It worth noting that, compared to the very recently published work, our DFT derived structure ( a = 9.5160 Å, b = 11.3986 Å, c = 17.8761 Å, β = 101.590°, S.G. C 2/ c ) matches closely with the GaS 2 framework moiety obtained through SC-XRD ( a = 10.2674(13) Å, b = 10.2681(12) Å, c = 18.090(2) Å, β = 98.457(3) °, S.G. C 2/ c ). The main difference between the two representations is in the choice of the unit cell, so that orientation-wise, the [−1 –1 0] of the SC-XRD and the [1 –1 0] of the DFT solutions yield an identical projection of the crystal structure (Figure S7).…”

Section: Resultssupporting

confidence: 85%

“…We find that water induced phase transformation influences the Na-ion conductivity in the lattice and could be used as a humidity sensor. During the preparation of our revised version of the manuscript, another publication appeared reporting hydration of NaGaS 2 and ion-exchange properties of this material …”

Section: Introductionmentioning

confidence: 99%

Unusual Atmospheric Water Trapping and Water Induced Reversible Restacking of 2D Gallium Sulfide Layers in NaGaS₂ Formed by Supertetrahedral Building Unit

et al. 2020

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Two new ternary materials NaGaS 2 (1) and the Fedoped phase of NaGaS 2 , NaFe 0.135 Ga 0.865 S 2 (2), have been synthesized by employing polysulfide flux. Single crystal XRD analyses of 1 and 2 show that the structure is built up of adamantane-like Ga 4 S 10 super tetrahedral fundamental building units. These admantane-like units are connected through their corners to form [GaS 2 ] ∞ − layers that are stacked one over the other with Na ions residing in between the layers to balance the charge. Both the materials have the remarkable ability to absorb atmospheric water molecules and moisture from undried solvents as verified by TG analysis and FT-IR and XPS studies. The process of water absorption leads to stable distinct material) with restacked layers different from original crystal structure. This structural transformation is reversible as the transformed structures 1•H 2 O and 2•H 2 O can be returned to their original structures 1 and 2, respectively, upon heating. DFT calculation study reveals that a spontaneous exergonic hydration reaction takes place as outlined in NaGaS 2 + H 2 O → NaGaS 2 •H 2 O with the energy release, ΔE of −73.9 kJ mol −1 . DFT calculation predicts an increase in the unit cell parameters of b and c directions and shrinkage along the a direction of hydrated phase 1•H 2 O with an overall volume increase of 36.6%. Structural transformation affects their physical properties as the pristine compound 1 possess Na + ion conductivity of 2.88 × 10 −7 S cm −1 at 22 °C, whereas the hydrated compound 1•H 2 O displays ∼40 times increased ion conductivity of 1.25 × 10 −5 S cm −1 at the same temperature. DRS studies show very similar optical band gaps of ∼4 eV for compounds 1 and 1•H 2 O, respectively, in reasonable agreement with the DFT(HSE) band gap estimation but more than 1 eV above the DFT(PBE)-predicted band gaps of ∼2.4 eV. A sorption study indicates selective adsorption of water over MeOH, EtOH, and CH 3 CN with a maximum water uptake of 2.6 H 2 O per formula unit at P/P 0 = 0.9. A Karl Fischer titration study shows that NaGaS 2 (1) is certainly capable of adsorbing water from wet methanol and can be useful as a fast desiccating agent.

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“…They exist in several structure types. The most known and the most well-studied is AGaS 2 (ANa, 14 Cs, 15 Ag 16–18 ) family of materials. Several novel members in this family, Na 6 Ga 2 S 6 19 and A 5 GaS 4 (ALi, Na), 20 were recently discovered.…”

Section: Introductionmentioning

confidence: 99%

“…A standard protocol for synthesizing the various ternary A x GaS y materials involves heating to 650–800 °C for several hours in the sealed quartz ampoule. 14,20 A few studies report the low-temperature synthesis route to alkali-containing ternary thiogallates, which is more advantageous for industrialization. For instance, AgGaS 2 18 was obtained at 300 °C under the N 2 atmosphere in the presence of oleates.…”

Section: Introductionmentioning

confidence: 99%

Ethane oxidative dehydrogenation with CO₂ on thiogallates

Bikbaeva

Pérez

Nesterenko

et al. 2022

Inorg. Chem. Front.

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NaGaS₂: An Elusive Layered Compound with Dynamic Water Absorption and Wide‐Ranging Ion‐Exchange Properties

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 19 publications

References 51 publications

Air Sensitivity and Degradation Evolution of Halide Solid State Electrolytes upon Exposure

Air Sensitivity and Degradation Evolution of Halide Solid State Electrolytes upon Exposure

Unusual Atmospheric Water Trapping and Water Induced Reversible Restacking of 2D Gallium Sulfide Layers in NaGaS₂ Formed by Supertetrahedral Building Unit

Ethane oxidative dehydrogenation with CO₂ on thiogallates

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NaGaS2: An Elusive Layered Compound with Dynamic Water Absorption and Wide‐Ranging Ion‐Exchange Properties

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 19 publications

References 51 publications

Air Sensitivity and Degradation Evolution of Halide Solid State Electrolytes upon Exposure

Air Sensitivity and Degradation Evolution of Halide Solid State Electrolytes upon Exposure

Unusual Atmospheric Water Trapping and Water Induced Reversible Restacking of 2D Gallium Sulfide Layers in NaGaS2 Formed by Supertetrahedral Building Unit

Ethane oxidative dehydrogenation with CO2 on thiogallates

Contact Info

Product

Resources

About

NaGaS₂: An Elusive Layered Compound with Dynamic Water Absorption and Wide‐Ranging Ion‐Exchange Properties

Unusual Atmospheric Water Trapping and Water Induced Reversible Restacking of 2D Gallium Sulfide Layers in NaGaS₂ Formed by Supertetrahedral Building Unit

Ethane oxidative dehydrogenation with CO₂ on thiogallates