Deciphering reduction stability of sulfone and fluorinated sulfone electrolytes:Insight from quantum chemical calculations

Du, Fuming; Tuo, Ye; Shi, Yimin; Zhang, Yong; Qiu, Ziyi; Liu, Wei; Lv, Tiezheng; Duan, S.Y.; Li, Jianjun

doi:10.1016/j.chemphys.2023.111840

Cited by 3 publications

(8 citation statements)

References 31 publications

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“…Du and his colleagues [61,62] conducted a calculation-based study to understand the oxidation process and degradation mechanisms of both fluorinated and non-fluorinated derivatives of TMS, EMS, PMS, and MIS in isolated environments, as well as in 1 m PF 6 − and FSI − solutions (Figure 6b,c). For fluorinated alkyl or cycloalkyl sulfones complexed with the PF 6 − anion, the oxidation potentials were calculated to be ≈0.2 V lower than those of the isolated sulfones.…”

Section: Correlation Of Organosulfur Structures and Their Electrochem...mentioning

confidence: 99%

“…Alternatively, fluorinated alkyl sulfones, if reducible at the anode, might simplify electrolyte design and allow for lower salt concentrations. In a subsequent study, Du and co-workers [62] attempted to rationalize the reducibility trends for the same set of fluorinated sulfones, as described in the study of Su et al, [8,60] based on solvating power and reduction potential. This provided insights into the regulation of interfacial solvation at the anode and the anticipated products that would yield fluorine-rich passivating layers.…”

Section: Correlation Of Organosulfur Structures and Their Electrochem...mentioning

confidence: 99%

“…d) Anion impact on the reduction potential of Li + -solvent complexes with respect to the reduction potential of the individual ion pairs of the salt. [62] Reproduced with permission. [62] Copyright 2021, Elsevier.…”

Section: Correlation Of Organosulfur Structures and Their Electrochem...mentioning

confidence: 99%

“…This difference can be rationalized by the electron-withdrawing groups (EWG) on the sulfonamides, which decrease their Lewis basicity and mitigate the dissolution of oxygen-based degrada-tion products from the cathode material. As a result, these structures are known for their high oxidative stability, typically well above 4.5 V. [43,44,49,50,62] It's important to note that there is relatively less research comparing the electrochemical properties of most sulfonamides listed in Table 1 with their electrochemical performance, as presented in Table 2. More studies are needed to evaluate and understand the electrochemical behavior and performance of these emerging fluorinated sulfonamides in practical battery applications.…”

Section: Correlation Of Organosulfur Structures and Their Electrochem...mentioning

confidence: 99%

“…They draw inspiration from the structures of imide stabilizing salts known for their robustness when paired with lithium metal anodes. [25,43,62] This natural compatibility with lithium salts like LiTFSI and LiFSI enables the creation of electrolyte compositions with intriguing properties that can effectively interface with highvoltage cathode materials while accommodating lithium metal anodes simultaneously.…”

Section: Sulfonamidesmentioning

confidence: 99%

See 4 more Smart Citations

Sulfur Solutions: Advancing High Voltage and High Energy Lithium Batteries with Organosulfur Electrolytes

Dato,

Edgington,

Hung

et al. 2024

Advanced Energy Materials

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Achieving energy densities exceeding 350 Wh kg−1 while operating at elevated voltages (>4.5 V vs Li/Li+) is attainable through judicious selection of electrochemical pairs at the cathode and anode. However, current state‐of‐the‐art electrolytes exhibit limited stability when exposed to systems operating at or above 4.3 V. This limitation contributes to the degradation of electrode materials and raises critical safety concerns, impeding the commercialization of such systems. Consequently, there has been a notable surge in research efforts aimed at developing innovative electrolyte compositions capable of supporting high‐voltage lithium‐ion batteries (LIBs). A substantial portion of this research has focused on the family of organosulfur molecules, which possess high oxidative stability. Organosulfur salts also facilitate the formation of dense, ionically conductive solid electrolyte interfaces (SEI) and demonstrate excellent solubility. This article provides a comprehensive overview of the field of organosulfur electrolyte components for their applications in energy storage, encompassing solvents, alternative conducting salts, and additives. It emphasizes the idea that the deliberate design of electrolyte compositions is instrumental in controlling electrode passivation, with organosulfur‐based structures historically proving advantageous in every aspect of the electrolyte. Crucially, it should be noted that many of these components are commercially available, holding significant implications for industrial applications.

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Section: Correlation Of Organosulfur Structures and Their Electrochem...mentioning

confidence: 99%

Section: Correlation Of Organosulfur Structures and Their Electrochem...mentioning

confidence: 99%

Section: Correlation Of Organosulfur Structures and Their Electrochem...mentioning

confidence: 99%

Section: Correlation Of Organosulfur Structures and Their Electrochem...mentioning

confidence: 99%

Section: Sulfonamidesmentioning

confidence: 99%

See 3 more Smart Citations

Sulfur Solutions: Advancing High Voltage and High Energy Lithium Batteries with Organosulfur Electrolytes

Dato,

Edgington,

Hung

et al. 2024

Advanced Energy Materials

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Constructing stable electrode–electrolyte interfaces by sulfone-based additive to improve the high-voltage performance of LiCoO2

Li,

Zou,

Xiao

et al. 2024

Journal of Alloys and Compounds

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Theoretical Study on Fluorinated Derivatives of Sulfolane, Cyclopentanone, and Gamma-Butyrolactone

Tshepelevitsh,

Kütt,

Leito

2023

Molecules

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In this paper, fluorinated compounds based on sulfolane, cyclopentanone, and gamma-butyrolactone are studied computationally, focusing on their applicability in electrochemical devices and acid–base-related studies. Candidates for solvents with (1) high polarity, (2) good electrochemical stability, and (3) low basicity were searched for. Some of the compounds are studied here for the first time. Electrochemical stabilities, dielectric constants, boiling points, basicities, and lipophilicities were estimated using DFT and COSMO-RS methods with empirical corrections. The effect of fluorination on these properties as well as the bond parameters was studied. The possible synthesis routes of the proposed compounds are outlined. Some molecules display a combination of estimated properties favorable for a solvent, although none of the studied compounds are expected to surpass acetonitrile and propylene carbonate by the width of the electrochemical stability window.

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Deciphering reduction stability of sulfone and fluorinated sulfone electrolytes:Insight from quantum chemical calculations

Cited by 3 publications

References 31 publications

Sulfur Solutions: Advancing High Voltage and High Energy Lithium Batteries with Organosulfur Electrolytes

Sulfur Solutions: Advancing High Voltage and High Energy Lithium Batteries with Organosulfur Electrolytes

Constructing stable electrode–electrolyte interfaces by sulfone-based additive to improve the high-voltage performance of LiCoO2

Theoretical Study on Fluorinated Derivatives of Sulfolane, Cyclopentanone, and Gamma-Butyrolactone

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