Nonflammable Trimethyl Phosphate Solvent-Containing Electrolytes for Lithium-Ion Batteries: II. The Use of an Amorphous Carbon Anode

Wang, Xianming; Yasukawa, Eiki; Kasuya, Shigeaki

doi:10.1149/1.1397774

Cited by 139 publications

(77 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…For instance, althoughT MP and DMMP are highly efficient FRs, they do not form as table SEI layer,w hich then has ad etrimentali mpact on the coulombic efficiency,a nd thus, the cycling stability. [138,143] Hence, the design of additives with high FR characteristics needs to comply with the formationo farobust SEI layer,a nd thereby, electrochemical compatibility.I nt he pursuit of alleviating the trade-off between flammability and cell performance, severalm ethods are effective, includinga ni ncrease in the alkyl chain length, [140] the development of fluorinated organophosphorus compounds, [144][145][146] the partial replacemento fa lkyl groups by aryl(phenyl) groups, [147,148] and the utilization of cyclic phosphates. [149] Fluorinated phosphates,f or instance, possess ac ouple of attractive features www.chemsuschem.org compared with non-fluorinated ones, showing, amongo ther things, ah ighly synergistic effect of both fluorine and phosphorusa nd enablingt he formationo fastable SEI on graphite anodes.…”

Section: Flame-retardant Additivesmentioning

confidence: 99%

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

et al. 2015

View full text Add to dashboard Cite

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.

show abstract

Section: Flame-retardant Additivesmentioning

confidence: 99%

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

et al. 2015

View full text Add to dashboard Cite

show abstract

“…114 It was found that the reduction decomposition of TMP solvent, which occurred without limit on a natural graphite anode and concomitantly generated a large amount of methane (CH 4 ) and ethylene (C 2 H 4 ) gases, was considerably suppressed on an amorphous carbon anode. The charge/discharge data and cyclic voltammetry indicated the formation of a highly stable and passivating surface film on the carbon surface at a potential near 1 V. In terms of safety, the ionic-liquid-based inorganic electrolyteLiBF4 in 1-ethyl-3-methylimidazolium tetra fluoroborate (EMI-BF4) -is one alternative because of its higher boiling point than that of LiPF 6 in EC/DEC and non-flammability.…”

Section: Carbonaceous Electrodesmentioning

confidence: 99%

Review—SEI: Past, Present and Future

Peled

Menkin

2017

J. Electrochem. Soc.

1,603

1,474

View full text Add to dashboard Cite

The Solid-Electrolyte-Interphase (SEI) model for non-aqueous alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the solution is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047Soc., 126, (1979.] new equations for: electrode kinetics (i o and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technology of lithium batteries. This paper reviews the past, present and the future of SEI batteries. The PastPrior to the publication of the SEI model (1979), 1,4 researchers used the Butler-Volmer equation, in which direct electron transfer from the electrode to lithium cations in the solution is assumed. It was generally assumed that the rate-determining step (RDS) is the transfer of electrons from the metal to the cations in the solution. Researchers found that the lithium anode is covered by a passivating layer which interferes with the deposition/dissolution process of the anode. Brummer and Newman 2,3 concluded that a passivating anode can offer only a limited cycle life and in order to obtain a deep-discharge high-cycle-life secondary battery, the lithium anode must be free of a passivating layer and kinetically stable with respect to the electrolyte. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, except when forming a SEI, must be prevented. The Present, Lithium-Metal and Lithium-Ion BatteriesIntroduction.-It is now generally accepted that the solidelectrolyte interphase (SEI) is essentially for the existence and successful operation of lithium-and sodium-battery systems, as primary and secondary power sources. 4 In 1979, it was proposed by Peled,

show abstract

“…One of the most immediate strategies to address the thermal safety of electrolytes is to lower the electrolyte inflammability by using flame retardants as additives or cosolvents [3][4][5][6][7][8][9][10][11][12][13][14]. Among the variety of flame retardant additives, organophosphates are commonly applied, due to their low viscosity and high solubility, such as trimethyl phosphate (TMP) [3][4][5], triethyl phosphate (TEP) [6], dimethyl methylphosphonate (DMMP) [7,11,15], diethyl ethylphosphonate (DEEP) [8], and so on.…”

Section: Introductionmentioning

confidence: 99%

“…Among the variety of flame retardant additives, organophosphates are commonly applied, due to their low viscosity and high solubility, such as trimethyl phosphate (TMP) [3][4][5], triethyl phosphate (TEP) [6], dimethyl methylphosphonate (DMMP) [7,11,15], diethyl ethylphosphonate (DEEP) [8], and so on. However, organophosphates have the drawbacks of lower flame retardant efficiency and poor electrochemical compatibility with electrode materials.…”

Section: Introductionmentioning

confidence: 99%