Effect of sulfolane and lithium bis(oxalato)borate-based electrolytes on the performance of spinel LiMn2O4 cathodes at 55 °C

Li, Shiyou; Yang, Xue; Cui, Xiaoling; Geng, Shujiang; Huang, Yuanzheng

doi:10.1007/s11581-015-1611-z

Cited by 8 publications

(7 citation statements)

References 22 publications

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“…This mechanism can complement the disproportionation reaction mechanism, and the structure instability of LMO at high voltage was confirmed by experiment . However, the electrolyte instability at high voltage is another issue that should be considered as it will promote TM dissolution. − The Choi group and Aoshima group proposed that Mn dissolution comes from Mn 4+ reduction by lithium salt and solvent at high voltage. This mechanism can explain the role of electrolyte in Mn dissolution at high voltage, but whether the reducing agent is lithium salt or solvent remains to be explored.…”

mentioning

confidence: 86%

Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn₂O₄ Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Zhuang

Sun

et al. 2020

J. Phys. Chem. Lett.

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The dissolution of transition-metal (TM) cations into a liquid electrolyte from cathode material, such as Mn ion dissolution from LiMn2O4 (LMO), is detrimental to the cycling performance of Li-ion batteries (LIBs). Though much attention has been paid to this issue, the behavior of Mn dissolution has not been clearly revealed. In this work, by using a refined in situ ultraviolet–visible (UV–vis) spectroscopy technique, we monitored the concentration changes of dissolved Mn ions in liquid electrolyte from LMO at different state of charge (SOC), confirming the maximum dissolution concentration and rate at 4.3 V charged state and Mn2+ as the main species in the electrolyte. Through ab initio molecular dynamics (AIMD) simulations, we revealed that the Mn dissolution process is highly related to surface structure evolution, solvent decomposition, and lithium salt. These results will contribute to understanding TM dissolution mechanisms at working conditions as well as the design of stable cathodes.

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mentioning

confidence: 86%

Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn₂O₄ Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Zhuang

Sun

et al. 2020

J. Phys. Chem. Lett.

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“…11,12 Therefore, LiBOB has become a popular component in electrolytes that aims to lower the fluorine content while increasing stability in electrolytes based on carbonates, 13−15 lactones, 16 and sulfones. 17 Furthermore, the strong passivating properties of LiBOB in traditional solvents also seem to persist when it is used in conjunction with nonflammable solvents like trimethyl phosphate (TMP) and dimethyl methyl phosphonate (DMMP). 18−20 Sodium bis(oxalate)borate (NaBOB) however has not received much attention after its synthesis was reported by Whittingham et al 21 since it was deemed insoluble in any common solvents such as carbonates and acetonitrile.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Bis-oxalato borate (BOB – ) is an alternative anion that has been extensively studied for lithium-ion batteries, − but it has only recently been investigated in sodium-ion batteries . Lithium bis(oxalate)borate (LiBOB) has shown to be a cost-effective salt with many attractive properties in terms of passivation of both graphite and aluminum. , Therefore, LiBOB has become a popular component in electrolytes that aims to lower the fluorine content while increasing stability in electrolytes based on carbonates, − lactones, and sulfones . Furthermore, the strong passivating properties of LiBOB in traditional solvents also seem to persist when it is used in conjunction with nonflammable solvents like trimethyl phosphate (TMP) and dimethyl methyl phosphonate (DMMP). − …”

Section: Introductionmentioning

confidence: 99%

A Wide-Temperature-Range, Low-Cost, Fluorine-Free Battery Electrolyte Based On Sodium Bis(Oxalate)Borate

et al. 2021

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Common battery electrolytes comprise organic carbonate solvents and fluorinated salts based on hexafluorophosphate (PF6 –) anions. However, these electrolytes suffer from high flammability, limited operating temperature window, and high cost. To address those issues, we here propose a fluorine-free electrolyte based on sodium bis(oxalate)borate (NaBOB). Although lithium bis(oxalate)borate (LiBOB) has previously been investigated for lithium-ion batteries, NaBOB was considered too insoluble in organic solvents to be used in practice. Here, we show that NaBOB can be dissolved in mixtures of N-methyl-2-pyrrolidone (NMP) and trimethyl phosphate (TMP) and in each sole solvent. NMP provides higher solubility of NaBOB with a concentration of almost 0.7 M, resulting in an ionic conductivity up to 8.83 mS cm–1 at room temperature. The physical and electrochemical properties of electrolytes based on NaBOB salt dissolved in NMP and TMP solvents and their binary mixtures are here investigated. The results include the thermal behavior of the sole solvents and their mixtures, flammability tests, NaBOB solubility, and ionic conductivity measurements of the electrolyte mixtures. Full-cell sodium-ion batteries based on hard carbon anodes and Prussian white cathodes were evaluated at room temperature and 55 °C using the aforementioned electrolytes. The results show a much improved performance compared to conventional electrolytes of 1 M NaPF6 in carbonate solvents at high currents and elevated temperatures. The proposed electrolytes provide a high ionic conductivity at a wide temperature range from room temperature to −60 °C as NMP–TMP mixtures have low freezing points. The flammability tests indicate that NaBOB in NMP–TMP electrolytes are nonflammable when the electrolyte contains more than 30 vol % TMP.

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“…Sulfolane has been used both as an additive [16] in conventional electrolytes to raise the oxidation potential of the electrolyte, but also as a sole aprotic solvent in the electrolyte [17,18] or used with a co-solvent. [19][20][21][22][23][24] Sulfolane exhibits a high boiling point of 287 °C, a flash point of 165 °C and a dielectric constant of > 40, primarily due to the oxygen in the sulfone group which is the coordinating motif to the lithium ion, and which triggers dissolution of lithium salts. [8,11,18] With respect to the conducting salt, lithium bis(fluorosulfonyl)imide (LiFSI) has a thermal stability of 200 °C and high solubility in organic solvents.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Electrochemical and Interfacial Behavior of Sulfolane based Electrolyte in LiNi_0.5Mn_1.5O₄‐Graphite Full‐Cells

Salian

Mathew

Gond

et al. 2023

Batteries & Supercaps

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An ethylene carbonate‐free electrolyte composed of 1 M lithium bis(fluorosulfonyl) imide (LiFSI) in sulfolane (SL) is studied here for LiNi0.5Mn1.5O4‐graphite full‐cells. An important focus on the evaluation of the anodic stability of the SL electrolyte and the passivation layers formed on LiNi0.5Mn1.5O4 (LNMO) and graphite is being analysed along with intermittent current interruption (ICI) technique to observe the resistance while cycling. The results show that the sulfolane electrolyte shows more degradation at higher potentials unlike previous reports which suggested higher oxidative stability. However, the passivation layers formed due to this electrolyte degradation prevents further degradation. The resistance measurements show that major resistance arises from the cathode. The pressure evolution during the formation cycles suggests that there is lower gas evolution with sulfolane electrolyte than in the conventional electrolyte. The study opens a new outlook on the sulfolane based electrolyte especially on its oxidative/anodic stability.

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Effect of sulfolane and lithium bis(oxalato)borate-based electrolytes on the performance of spinel LiMn2O4 cathodes at 55 °C

Cited by 8 publications

References 22 publications

Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn₂O₄ Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn₂O₄ Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

A Wide-Temperature-Range, Low-Cost, Fluorine-Free Battery Electrolyte Based On Sodium Bis(Oxalate)Borate

Understanding the Electrochemical and Interfacial Behavior of Sulfolane based Electrolyte in LiNi_0.5Mn_1.5O₄‐Graphite Full‐Cells

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Effect of sulfolane and lithium bis(oxalato)borate-based electrolytes on the performance of spinel LiMn2O4 cathodes at 55 °C

Cited by 8 publications

References 22 publications

Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn2O4 Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn2O4 Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

A Wide-Temperature-Range, Low-Cost, Fluorine-Free Battery Electrolyte Based On Sodium Bis(Oxalate)Borate

Understanding the Electrochemical and Interfacial Behavior of Sulfolane based Electrolyte in LiNi0.5Mn1.5O4‐Graphite Full‐Cells

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Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn₂O₄ Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn₂O₄ Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Understanding the Electrochemical and Interfacial Behavior of Sulfolane based Electrolyte in LiNi_0.5Mn_1.5O₄‐Graphite Full‐Cells