Synthesis, modular composition, and electrochemical properties of lamellar iron sulfides

Horwitz, Noah E.; Shevchenko, Elena V.; Park, Jehee; Lee, Eungje; Xie, Jiaze; Chen, Baorui; Zhong, Yu; Filatov, Alexander S.; Anderson, John S.

doi:10.1039/d0ta00689k

Cited by 12 publications

(10 citation statements)

References 98 publications

(115 reference statements)

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“…43 Another possibility is that the intermediate species could represent a poorly ordered lamellar iron sulfide which bears similarity to the mackinawite structure and has recently been reported to reversibly intercalate solvated lithium ions. 44 We note that both of these structures feature a tetrahedrally coordinated iron which is consistent with previous synchrotron studies that characterized the Fe Kedge of the intermediate phase. 32 While more studies are needed to identify the exact structure of the intermediate species, we propose that the intermediate region involves Li insertion/extraction 32 into/out of a mackinawite-based structure (Li x FeS) at 60 °C (eq 4).…”

Section: ■ Resultssupporting

confidence: 90%

Temperature-Dependent Reaction Pathways in FeS₂: Reversibility and the Electrochemical Formation of Fe₃S₄

et al. 2022

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The present study has used a variety of characterization techniques to determine the products and reaction pathways involved in the rechargeable Li−FeS 2 system. We revisit both the initial lithiation and subsequent cycling of FeS 2 employing an ionic liquid electrolyte to investigate the intermediate and final charge products formed under varying thermal conditions (room temperature to 100 °C). The detection of Li 2 S and hexagonal FeS as the intermediate phases in the initial lithiation and the electrochemical formation of greigite, Fe 3 S 4 , as a charge product in the rechargeable reaction differ significantly from previous reports. The conditions for Fe 3 S 4 formation are shown to be dependent on both the temperature (∼60 °C) and the availability of sulfur to drive a FeS to Fe 3 S 4 transformation. Upon further cycling, Fe 3 S 4 transforms to a lower sulfur content iron sulfide phase, a process which coincides with the loss of sulfur based on the new reaction pathways established in this work. The connection between sulfur loss, capacity fade, and charge product composition highlights the critical need to retain sulfur in the active material upon cycling.

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Section: ■ Resultssupporting

confidence: 90%

Temperature-Dependent Reaction Pathways in FeS₂: Reversibility and the Electrochemical Formation of Fe₃S₄

et al. 2022

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“…Novel lamellar iron sulfides result from the solvothermal decomposition of [Fe(S 2 CNEt 2 ) 3 ] in the presence of lithium triflate (DMF at 140 °C for 3 d), a stoichiometry of Fe 0.77 SLi 0.090 (DMF,THF) 0.19 being established, and related lamellar materials can also be prepared with other triflate salts, M(SO 3 CF 3 ) (M = Na, K) and [Me 4 N]PF 6 . 151 PXRD studies suggest that these materials are poorly ordered and have lamellar spacings consistent with intercalation of solvated cations; the lithium materials have interlayer distances of ca. 10.5 Å.…”

Section: Groupmentioning

confidence: 99%

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

2021

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Nanodimensional metal sulfides are a developing class of low-cost materials with potential applications in areas as wide-ranging as energy storage, electrocatalysis, and imaging. An attractive synthetic strategy, which allows careful control over stoichiometry, is the single source precursor (SSP) approach in which well-defined molecular species containing preformed metal–sulfur bonds are heated to decomposition, either in the vapor or solution phase, resulting in facile loss of organics and formation of nanodimensional metal sulfides. By careful control of the precursor, the decomposition environment and addition of surfactants, this approach affords a range of nanocrystalline materials from a library of precursors. Dithiocarbamates (DTCs) are monoanionic chelating ligands that have been known for over a century and find applications in agriculture, medicine, and materials science. They are easily prepared from nontoxic secondary and primary amines and form stable complexes with all elements. Since pioneering work in the late 1980s, the use of DTC complexes as SSPs to a wide range of binary, ternary, and multinary sulfides has been extensively documented. This review maps these developments, from the formation of thin films, often comprised of embedded nanocrystals, to quantum dots coated with organic ligands or shelled by other metal sulfides that show high photoluminescence quantum yields, and a range of other nanomaterials in which both the phase and morphology of the nanocrystals can be engineered, allowing fine-tuning of technologically important physical properties, thus opening up a myriad of potential applications.

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“…Mackinawite—an electron conductor [ 176 ]—is the subordinate sulfide analogue of fougerite, precipitating with it at the submarine alkaline spring, and comprising a small inner portion of the membranes dividing ocean from alkaline hydrothermal solution ( Figure 5 ) [ 56 , 177 ]. Although, like fougerite it is a layered mineral, Bourdoiseau and coworkers [ 178 ] have shown, against earlier expectations, that it includes no layered hydrous intercalations.…”

Section: Two Minerals To Make Life Happenmentioning

confidence: 99%

Six ‘Must-Have’ Minerals for Life’s Emergence: Olivine, Pyrrhotite, Bridgmanite, Serpentine, Fougerite and Mackinawite

Russell

Ponce

2020

Life

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Life cannot emerge on a planet or moon without the appropriate electrochemical disequilibria and the minerals that mediate energy-dissipative processes. Here, it is argued that four minerals, olivine ([Mg>Fe]2SiO4), bridgmanite ([Mg,Fe]SiO3), serpentine ([Mg,Fe,]2-3Si2O5[OH)]4), and pyrrhotite (Fe(1−x)S), are an essential requirement in planetary bodies to produce such disequilibria and, thereby, life. Yet only two minerals, fougerite ([Fe2+6xFe3+6(x−1)O12H2(7−3x)]2+·[(CO2−)·3H2O]2−) and mackinawite (Fe[Ni]S), are vital—comprising precipitate membranes—as initial “free energy” conductors and converters of such disequilibria, i.e., as the initiators of a CO2-reducing metabolism. The fact that wet and rocky bodies in the solar system much smaller than Earth or Venus do not reach the internal pressure (≥23 GPa) requirements in their mantles sufficient for producing bridgmanite and, therefore, are too reduced to stabilize and emit CO2—the staple of life—may explain the apparent absence or negligible concentrations of that gas on these bodies, and thereby serves as a constraint in the search for extraterrestrial life. The astrobiological challenge then is to search for worlds that (i) are large enough to generate internal pressures such as to produce bridgmanite or (ii) boast electron acceptors, including imported CO2, from extraterrestrial sources in their hydrospheres.

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Synthesis, modular composition, and electrochemical properties of lamellar iron sulfides

Abstract: A new class of layered iron sulfide materials offers tunable composition and properties for electrochemical energy storage.

Cited by 12 publications

References 98 publications

Temperature-Dependent Reaction Pathways in FeS₂: Reversibility and the Electrochemical Formation of Fe₃S₄

Temperature-Dependent Reaction Pathways in FeS₂: Reversibility and the Electrochemical Formation of Fe₃S₄

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

Six ‘Must-Have’ Minerals for Life’s Emergence: Olivine, Pyrrhotite, Bridgmanite, Serpentine, Fougerite and Mackinawite

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Synthesis, modular composition, and electrochemical properties of lamellar iron sulfides

Abstract: A new class of layered iron sulfide materials offers tunable composition and properties for electrochemical energy storage.

Cited by 12 publications

References 98 publications

Temperature-Dependent Reaction Pathways in FeS2: Reversibility and the Electrochemical Formation of Fe3S4

Temperature-Dependent Reaction Pathways in FeS2: Reversibility and the Electrochemical Formation of Fe3S4

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

Six ‘Must-Have’ Minerals for Life’s Emergence: Olivine, Pyrrhotite, Bridgmanite, Serpentine, Fougerite and Mackinawite

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Temperature-Dependent Reaction Pathways in FeS₂: Reversibility and the Electrochemical Formation of Fe₃S₄

Temperature-Dependent Reaction Pathways in FeS₂: Reversibility and the Electrochemical Formation of Fe₃S₄