Effects of gamma radiation on electrochemical properties of ionic liquids

Bridges, Nicholas J.; Visser, Ann E.; Williamson, Mark J.; Mickalonis, J.I.; Adams, Thad M.

doi:10.1524/ract.2010.1704

Cited by 10 publications

(9 citation statements)

References 18 publications

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“…On irradiation, almost no change occurs in the electrochemical window of [EMIM][FAP], while marginal variations could be observed in the case of [EOHMIM][FAP] with an increase in the radiation dose, as shown in Table 5. Nevertheless, these changes are much smaller as compared to that reported earlier 10,55 for the irradiated ILs containing halides, BF…”

Section: It Is Seen That the [Emim][fap] Possesses A Wider Electroche...contrasting

confidence: 60%

“…Owing to the inherent wide electrochemical window and the ability to tune the nature of the cation and the anion for specific purposes, RTILs are considered the most promising solvents for the replacement of traditional organic solvents in various areas. 55 Several studies have been carried out in which mostly imidazolium based ILs containing fluoroanions such as PF 6 − , BF 4 − , or NTf 2 − were used in different stages of the nuclear fuel cycle. 56 However, BF 4 − and PF 6 − are susceptible to hydrolysis as well as decomposition.…”

Section: The Conductivity Of [Emim]mentioning

confidence: 99%

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Radiation induced physicochemical changes in FAP (fluoro alkyl phosphate) based imidazolium ionic liquids and their mechanistic pathways: influence of hydroxyl group functionalization of the cation

et al. 2014

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Future applications of ionic liquids (ILs) in a variety of areas, especially those having high radiation fields such as the nuclear fuel cycle and in space technology, are under serious consideration nowadays. For such applications to be possible, however, radiation stability of the ILs is an important issue that needs to be addressed. We envisaged that the ultra-hydrophobic, bulky and hydrolytically stable FAP (tris(perfluoroalkyl)trifluorophosphate) anion might shield the radiolytically vulnerable imidazolium cations from degradation and our result shows that these anions indeed enhance their radiolytic stability. However, introduction of a hydroxyl group into the alkyl side chain of the imidazolium moiety resulted in significant changes in the physical properties of the IL with respect to onset temperatures, conductivity and the electrochemical window. Furthermore, a nonlinear trend in absorbance with an increase in radiation dose accompanied by NMR (nuclear magnetic resonance) and mass spectrometry studies clearly demonstrated that the presence of the hydroxyl group promotes various degradation channels. Interestingly, a perturbation of the hydrogen bond between the hydroxyl group (present in the side chain of the cation) and the fluorine atom of the anion (OHF) was evident in the case of irradiated hydroxyl functionalized FAP ILs. Besides, the hydrogen gas yields of the ILs were determined and found to be comparable to those of a radiolytically stable aromatic compound, benzene. Finally, through transient spectroscopic studies we could delineate the mechanism of the radiation induced changes in the physicochemical properties of the non-hydroxyl and hydroxyl containing FAP ILs. We have clearly demonstrated that a simple functionalization of the molecular structure of the FAP based imidazolium ILs might cause marked differences in the reactivity, reaction center and the nature of the radiolytic products, which eventually lead to significant changes in their physicochemical properties.

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Section: It Is Seen That the [Emim][fap] Possesses A Wider Electroche...contrasting

confidence: 60%

Section: The Conductivity Of [Emim]mentioning

confidence: 99%

Radiation induced physicochemical changes in FAP (fluoro alkyl phosphate) based imidazolium ionic liquids and their mechanistic pathways: influence of hydroxyl group functionalization of the cation

et al. 2014

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“…[bmim][Tf 2 N], and [N 1114 ][Tf 2 N] found the same bathochromic shift, but no noticeable peaks in this wavelength region. 56 That work used open containers for the irradiations in order to avoid gas buildup. The presence of oxygen probably quenched normal radical reactions and modified product outcome from that found here.…”

Section: Resultsmentioning

confidence: 99%

Hydrogen Production in Aromatic and Aliphatic Ionic Liquids

et al. 2013

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The radiolytic production of molecular hydrogen in the ionic liquids N-trimethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide ([N1114][Tf2N]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) has been examined with γ-rays, 2-10 MeV protons, and 5-20 MeV helium ions to determine the functional dependence of the yield on particle track structure. Molecular hydrogen is the dominant gaseous radiolysis product from these ionic liquids, and the yields with γ-rays are 0.73 and 0.098 molecules per 100 eV of energy absorbed for [N1114][Tf2N] and [emim][Tf2N], respectively. These low yields are consistent with the relative insensitivity of most aromatic compounds to radiation. However, the molecular hydrogen yields increase considerably on going from γ-rays to protons to helium ions with [emim][Tf2N] while they remain essentially constant for [N1114][Tf2N]. FTIR and UV-vis spectroscopic studies show slight degradation of the ionic liquids with radiation.

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“…6 17 Other researchers have reported on the stability of quaternary ammonium cations, especially in the presence of lithium salts, such that the cathodic limit allows for battery research to be pursued using [N 4,1,1,1 ][Tf 2 N]. 13,16,18 At the potentials used for plating and stripping Li, currents observed in the experimental setup can approach or slightly exceed AE5 mA.…”

Section: Direct Injection Mass Spectrometry (Di-ms)mentioning

confidence: 99%

“…An earlier report had shown electrochemical windows for a variety of ILs and a lower cathodic limit of À2.6 V for [N 4,1,1,1 ][Tf 2 N] in comparison to À2.4 V for [C 4,1 pyrr][Tf 2 N], vs. ferrocene couple. 17 Other researchers have reported on the stability of quaternary ammonium cations, especially in the presence of lithium salts, such that the cathodic limit allows for battery research to be pursued using [N 4,1,1,1 ][Tf 2 N]. 13,16,18 At the potentials used for plating and stripping Li, currents observed in the experimental setup can approach or slightly exceed AE5 mA.…”

Section: Direct Injection Mass Spectrometry (Di-ms)mentioning

confidence: 99%

Electrochemical degradation of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide for lithium battery applications

et al. 2014

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Ionic liquids (ILs) are being considered as electrolytes for lithium ion batteries due to their low volatility, high thermal stability, and wide electrochemical windows which are stable at the strongly reducing potentials present in Li/Li + batteries. Lithium metal deposition occurs under strongly reducing conditions and the effect that Li metal and any overpotential has on the stability of ILs is important in furthering the application of ILs in lithium based batteries. Here, N-butyl-N-trimethylammonium bis(trifluoromethylsulfonyl)imide was exposed to various potential differences in order to collect and characterize the volatile products. The IL produced more volatile products when exposed to strong reducing potentials which included reactive products such as hydrogen, alkanes, and amines. Water is a known contributor to hydrogen production in reducing environments, but the IL is also a source of hydrogen. If Li + was present, the preferred pathway of reduction was plating of the lithium onto the working electrode, thus decreasing the reaction rate of degraded ILs.

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Effects of gamma radiation on electrochemical properties of ionic liquids

Cited by 10 publications

References 18 publications

Radiation induced physicochemical changes in FAP (fluoro alkyl phosphate) based imidazolium ionic liquids and their mechanistic pathways: influence of hydroxyl group functionalization of the cation

Radiation induced physicochemical changes in FAP (fluoro alkyl phosphate) based imidazolium ionic liquids and their mechanistic pathways: influence of hydroxyl group functionalization of the cation

Hydrogen Production in Aromatic and Aliphatic Ionic Liquids

Electrochemical degradation of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide for lithium battery applications

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