Sulfur X-ray Absorption and Emission Spectroscopy of Organic Sulfones

Vogt, Linda; Cotelesage, Julien J. H.; Dolgova, Natalia V.; Boyes, Curtis; Qureshi, Muhammad; Sokaras, Dimosthenis; Sharifi‐Asl, Samin; George, Simon J.; Pickering, Ingrid J.; George, Graham N.

doi:10.1021/acs.jpca.2c08647

Cited by 3 publications

(2 citation statements)

References 87 publications

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“…Specifically, sulfonyl species dominate after 30 cycles, while more reduced sulfur components, such as trace amount of Li 2 S emerge after 100 cycles, suggesting the further reduction of FSI − on the anode surface. 16 To elucidate SEI formation from the F5DEE electrolyte decomposition, atomistic models were used to investigate interfacial electrochemistry. Ab initio molecular dynamics (AIMD) simulations showed spontaneous dissociation of F5DEE and LiFSI on Li(100) surfaces, with electronegative atoms (O and F) coordinating with Li + .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Furthermore, the sulfur species in the interphase kept evolving during the electrochemical cycling, as suggested by the peak growth in the lower energy region (below 2480 eV). Specifically, sulfonyl species dominate after 30 cycles, while more reduced sulfur components, such as trace amount of Li 2 S emerge after 100 cycles, suggesting the further reduction of FSI – on the anode surface …”

Section: Resultsmentioning

confidence: 99%

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Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies

Tan,

Kuai,

et al. 2024

J. Am. Chem. Soc.

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Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of the lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron X-ray, which has the unique capability of analyzing crystalline/amorphous phases quantitatively with statistical significance, we study the composition and dynamics of the LMB interphase for a newly developed important LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential roles of the anion and solvent in interphase formation during cycling. The relative ratio between Li 2 O and LiF first increases and then decreases during cycling, suggesting suppressed Li 2 O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barriers in many-electron transfer. In long extended cycles, the anion decomposition product Li 2 O encourages solvent decomposition by facilitating solvent adsorption on Li 2 O which is followed by concurrent depletion of both. This work highlights the important role of Li 2 O in transitioning from an anion-derived interphase to a solvent-derived one.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies

Tan,

Kuai,

et al. 2024

J. Am. Chem. Soc.

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Interaction of disulfides with metal ions and spectroscopic identification of the products

Petrov

2024

Coordination Chemistry Reviews

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Metal–Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering

Larsen,

Ledbetter,

Nascimento

et al. 2024

J. Am. Chem. Soc.

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Metallo dithiolene complexes with biological and catalytic relevance are well-known for having strong metal−ligand covalency, which dictates their valence electronic structures. We present the resonant sulfur Kβ (1s3p) X-ray emission spectroscopy (XES) for a series of Ni and Cu bis(dithiolene) complexes to reveal the ligand sulfur contributions to both the occupied and unoccupied valence orbitals. While S K-edge X-ray absorption spectroscopy played a critical role in identifying the covalency of the unoccupied orbitals of metal dithiolenes, the present focus on XES explores the occupied density of states. For a series of [Cu(mnt) 2 ] n− and [Ni(mnt) 2 ] n− anions and dianions, a comparison of the nonresonant and resonant S Kβ XES spectra highlights the dramatic improvement in spectral resolution and corresponding ability to differentiate subtle changes in occupied electronic structure across the series. Furthermore, the use of resonant inelastic X-ray scattering (RIXS) probes the valence excited states and the core−valence couplings of the complexes. By employing a theoretical approach based on time-dependent density functional theory to interpret the RIXS spectra, we reveal how metal−ligand covalency influences the excited state energies and covalencies. We identify the low energy excited states as having the same symmetry as the nominal "ligand field" or "d−d" states that typically dominate the photophysics of 3d metal complexes but with significant metal− ligand charge transfer character dictated by their covalency. These results suggest that strong metal−ligand covalency can be used to influence the charge-transfer photochemistry of first row transition metal complexes.

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Sulfur X-ray Absorption and Emission Spectroscopy of Organic Sulfones

Cited by 3 publications

References 87 publications

Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies

Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies

Interaction of disulfides with metal ions and spectroscopic identification of the products

Metal–Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering

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