Thermal Stability and Electrochemical Properties of Fluorine Compounds as Nonflammable Solvents for Lithium-Ion Batteries

Achiha, Takashi; Nakajima, Tsuyoshi; Ohzawa, Yoshimi; Koh, Meiten; Yamauchi, Akiyoshi; Kagawa, Michiru; Aoyama, Hirokazu

doi:10.1149/1.3377084

Cited by 86 publications

(81 citation statements)

References 38 publications

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“…The improved stabilityt owards oxidation renders such fluorinated, cyanated, or sulfonated solvents advantageous, particularly with respectt oc ell overcharge. Additionally,t he reduced stability towards reduction may have ab eneficial effect on the SEI formation, [25,27] and thus, on safety.…”

Section: Alternative Organic Electrolyte Solventsmentioning

confidence: 99%

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

et al. 2015

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Lithium-ion batteries are becoming increasingly important for electrifying the modern transportation system and, thus, hold the promise to enable sustainable mobility in the future. However, their large-scale application is hindered by severe safety concerns when the cells are exposed to mechanical, thermal, or electrical abuse conditions. These safety issues are intrinsically related to their superior energy density, combined with the (present) utilization of highly volatile and flammable organic-solvent-based electrolytes. Herein, state-of-the-art electrolyte systems and potential alternatives are briefly surveyed, with a particular focus on their (inherent) safety characteristics. The challenges, which so far prevent the widespread replacement of organic carbonate-based electrolytes with LiPF6 as the conducting salt, are also reviewed herein. Starting from rather "facile" electrolyte modifications by (partially) replacing the organic solvent or lithium salt and/or the addition of functional electrolyte additives, conceptually new electrolyte systems, including ionic liquids, solvent-free, and/or gelled polymer-based electrolytes, as well as solid-state electrolytes, are also considered. Indeed, the opportunities for designing new electrolytes appear to be almost infinite, which certainly complicates strict classification of such systems and a fundamental understanding of their properties. Nevertheless, these innumerable opportunities also provide a great chance of developing highly functionalized, new electrolyte systems, which may overcome the afore-mentioned safety concerns, while also offering enhanced mechanical, thermal, physicochemical, and electrochemical performance.

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Section: Alternative Organic Electrolyte Solventsmentioning

confidence: 99%

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

et al. 2015

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“…2. These molecules have traditionally been used in specialized applications such as coolants and supercapacitors, and their use in Li-ion batteries is relatively new [5,6,74,78]. Regardless, these molecules have shown increased stability toward oxidation, better thermal stability, and low flammability.…”

Section: Fluorinated Carbonatesmentioning

confidence: 99%

“…Thus, fluorinated carbonates, especially linear carbonates, are excellent candidates for the low-temperature Li-ion batteries for space and deep-sea missions. Last but not least, the low-flammability to non-flammability of fluorinated compounds could potentially improve the safety of Li-ion batteries [5,6].…”

Section: Fluorinated Carbonatesmentioning

confidence: 99%

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Electrolytes for Lithium and Lithium-Ion Batteries

Zhang

2015

Rechargeable Batteries

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“…13,19 Fluoroether-containing electrolytes have been reported by other groups to enhance the performance of the Liion battery due to their unique physical and chemical properties; [20][21][22][23] however, it is our idea to use it as an electrolyte co-solvent/additive for the Li-S battery. In this paper, we report the self-discharge characteristics of Li-S battery with the fluorinated electrolyte containing 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE).…”

mentioning

confidence: 99%

Fluorinated Electrolytes for Li-S Battery: Suppressing the Self-Discharge with an Electrolyte Containing Fluoroether Solvent

Azimi

Xue

Rago

et al. 2014

J. Electrochem. Soc.

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The fluorinated electrolyte containing a fluoroether 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) was investigated as a new electrolyte for lithium-sulfur (Li-S) batteries. The low solubility of lithium polysulfides (LiPS) in the fluorinated electrolyte reduced the parasitic reactions with Li anode and mitigated the self-discharge by limiting their diffusion from the cathode to the anode. The use of fluorinated ether as a co-solvent and LiNO 3 as an additive in the electrolyte shows synergetic effect in suppressing the self-discharge of Li-S battery due to the formation of the solid electrolyte interphase (SEI) on both sulfur cathode and the lithium anode. The Li-S cell with the fluorinated electrolyte showed prolonged shelf life at fully charged state. Lithium-sulfur (Li-S) batteries are considered to be promising candidates which can satisfy the demand for high energy density batteries in electronic and transportation devices due to their high theoretical capacity, intrinsic overcharge protection, low cost and nontoxicity. 1,2 Sulfur, one of the most abundant elements in the earth's crust, has a theoretical capacity value of 1675 mAh/g and is the cheapest solid state cathode material for energy storage devices.Despite the considerable advantages, there are several major issues that impede the practical applications of the Li-S battery.3 Sulfur undergoes a series of structural and morphological changes during charge and discharge, which results in the formation of soluble Li 2 S x (4 < x < 8) and insoluble Li 2 S 2 and Li 2 S. The formation of soluble lithium polysulfides (LiPS) and their chemical reaction with the electrolyte and lithium anode leads to low coulombic efficiency and rapid capacity fading. [4][5][6][7] In addition, Li-S battery suffers from severe self-discharge, which is the biggest hurdle for the commercialization of this battery. 8 A secondary battery will lose charge capacity when stored for a period of time at a certain temperature. This behavior is known as self-discharge and depends on the battery chemistry, electrode composition, choice of current collector, electrolyte formulation, and the storage temperature. For Li-S batteries, the self-discharge is a well-known issue due to the severe corrosion of lithium metal anode in the presence of the LiPS in the electrolyte. 5,6,8 Many attempts have been made to overcome the poor cycle life and low sulfur utilization of Li-S batteries.7-14 However, there are only a few publications focused on solving the self-discharge issue of the Li-S battery. Kazazi et al. have reported that the corrosion of the aluminum current collector and the shuttle mechanism play a significant role in the self-discharge of Li-S cells; therefore, LiNO 3 is a suitable electrolyte additive candidate to prevent self-discharge due to its effect on shuttle prevention.8 Mikhaylik and Akridge reported that self-discharge mainly attributed from the high plateau polysulfides. Electrolytes with higher salt concentration also showed lower rates of Li corrosion wit...

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Thermal Stability and Electrochemical Properties of Fluorine Compounds as Nonflammable Solvents for Lithium-Ion Batteries

Cited by 86 publications

References 38 publications

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

Safer Electrolytes for Lithium‐Ion Batteries: State of the Art and Perspectives

Electrolytes for Lithium and Lithium-Ion Batteries

Fluorinated Electrolytes for Li-S Battery: Suppressing the Self-Discharge with an Electrolyte Containing Fluoroether Solvent

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