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

Klug, Christopher L.; Bridges, Nicholas J.; Visser, Ann E.; Crump, Stephen L.; Villa‐Aleman, Eliel

doi:10.1039/c4nj00355a

Cited by 5 publications

(5 citation statements)

References 23 publications

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“…To quantify the effect of J cut-off on the electrochemical limits systematically, five replicates of the current-voltage curve were measured in this work for a variety of electrolytes and ionic liquids. They were chosen because they are all commonly used in electroanalytical devices 22,23,[29][30][31] and electrochemical capacitors 3,6,7,32 due to their wide electrochemical windows. The electrochemical limits were determined based on J cut-off values of 0.5, 1.0, and 5.0 mA/cm 2 and are listed in Table I.…”

Section: Resultsmentioning

confidence: 99%

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Unbiased Quantification of the Electrochemical Stability Limits of Electrolytes and Ionic Liquids

Mousavi

Dittmer

Wilson

et al. 2015

J. Electrochem. Soc.

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The electrochemical window is the potential range in which an electrolyte/solvent system does not get reduced or oxidized. Usually, voltammograms are measured, and the potentials at which specific current densities are reached are identified as the electrochemical limits. We measured electrochemical limits of several electrolytes-including ionic liquids-and show that this approach has disadvantages that can be overcome by an alternate approach of defining electrochemical limits. The choice of the cutoff current density, J cut-off , is arbitrary and strongly affects the determined electrochemical windows, which are strongly influenced by electrolyte mass transport. Moreover, the J cut-off method does not provide an accurate estimate of the electrochemical window at electrodes with high surface areas, where the capacitive currents are large. We propose a method that requires no definition of J cut-off . This method minimizes electrolyte mass transport effects, gives realistic electrochemical stability limits at high surface area electrodes, and is less affected by experimental parameters such as the scan rate. The method is based on linear fits of the current-voltage curve at potentials below and above the onset of electrolyte decomposition. The potential at which the two linear fits intersect is defined as the electrolyte electrochemical limit. Electrolytes and solvents are essential for the proper function of a variety of electrochemical devices, such as batteries and supercapacitors. The voltage polarization in these devices can cause electrochemical degradation of the electrolyte and solvent, resulting in device malfunction. This can be avoided by constraining the working range of the device to the electrochemical window limited by the electrolyte and solvent, i.e., the potential range in which they are chemically stable and do not get reduced or oxidized.1,2 Due to their localized charges, the inherently ionic electrolytes often have a lower electrochemical stability than neutral solvent molecules, and therefore frequently limit the device working range.2 There has been extensive research on modifying the structure of electrolytes to improve their electrochemical stability, and thus expanding their working range. [3][4][5][6][7] The determination of the electrochemical window of electrolytes is not well defined. Generally a current-voltage polarization curve is measured, starting at a voltage at which the electrolyte is electrochemically stable, followed by increasing or decreasing the potential to observe the anodic or cathodic decompositions, respectively. The potential at which a specific current density, J, is reached is defined as the cathodic or anodic limit of the electrolyte. This approach has several disadvantages, as noted by several researchers.3-5 Firstly, since the choice of the cut-off current density is arbitrary, different standards have been applied in the literature. Cut-off current densities, J cut-off , in the range of 0.01 to 5.0 mA/cm 2 were reported, 3,7-20 resulting in electrochemical ...

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Section: Resultsmentioning

confidence: 99%

“…They were chosen because they are all commonly used in electroanalytical devices 22,23,[29][30][31] and electrochemical capacitors 3,6,7,32 due to their wide electrochemical windows. The electrochemical limits were determined based on J cut-off values of 0.5, 1.0, and 5.0 mA/cm 2 and are listed in Table I.…”

Section: Resultsmentioning

confidence: 99%

Unbiased Quantification of the Electrochemical Stability Limits of Electrolytes and Ionic Liquids

Mousavi

Dittmer

Wilson

et al. 2015

J. Electrochem. Soc.

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“…[8] The electrochemical stability of am ediumc an be evaluated by the width of its electrochemical potential window.F or imidazolium-based ionic liquids, it is typicallyl imited by the reduction of the cation and the oxidation of the anion. [10,16,17] Several studies report on the electrochemical stability of ionic liquids [15,[18][19][20][21][22][23][24][25][26][27][28][29][30][31] and especially neat imidazolium-based ionic liquids [15,21,[23][24][25] at very negative potentials. [10,16,17] Several studies report on the electrochemical stability of ionic liquids [15,[18][19][20][21][22][23][24][25][26][27][28][29][30][31] and especially neat imidazolium-based ionic liquids [15,21,[23][24][25] at very negative po...…”

Section: Introductionmentioning

confidence: 99%

“…[1,2,[9][10][11][12][13][14][15][16] It depends of course on the ionic species [1,2,10,12,13,16] but also on the material of the working electrode [2,[10][11][12][13][14] and on the presence of impuritiesincluding water. [10,16,17] Several studies report on the electrochemical stability of ionic liquids [15,[18][19][20][21][22][23][24][25][26][27][28][29][30][31] and especially neat imidazolium-based ionic liquids [15,21,[23][24][25] at very negative potentials. They mainly rely on quantum chemical calculations [15,21] or experimental investigations by NMR, [21,24,…”

Section: Introductionmentioning

confidence: 99%

NMR Study of the Reductive Decomposition of [BMIm][NTf₂] at Gold Electrodes and Indirect Electrochemical Conversion of CO₂

et al. 2017

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Potential controlled electrolyses of [BMIm][NTf ] ionic liquid were performed at a gold cathode under nitrogen atmosphere. The structures of the major conversion products of the BMIm cation were elucidated on the basis of 1D and 2D nuclear magnetic resonance (NMR) analyses and gas chromatography (GC) analysis of the volatile compounds. Recombination of the imidazol-2-yl radicals, generated at the electrode by single electron transfer, leads to neutral diastereomeric dimers in equal proportions, with a faradaic efficiency of 80 %, while disproportionation of these radicals and/or reaction with hydrogen atoms adsorbed at the electrode generates a neutral monomer with 20 % faradaic efficiency. Both pathways also yield the N-heterocyclic carbene imidazolin-2-ylidene, which is involved in fast proton exchange with the parent BMIm cation. The reductive decomposition products of the BMIm cation are no longer detected if the pre-electrolysed sample is reacted with CO , which undergoes an indirect reduction and generates the carboxylate adduct.

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“…2269 cm -1 , and v (CO2(g)): 2350 cm -1 . [51][52][53] In the case of Cu-BTC, an extra band was observed D r a f t corresponding to v (NO2(g)): 1614 cm -1 . 54,55 This may be attributed to the oxidizing ability of Cu for NO(g) in Cu-BTC, which is responsible for the presence of NO 2 species in the gas phase spectra.…”

Section: R a F Tmentioning

confidence: 98%

Mechanistic studies on the conversion of NO gas on urea-iron and copper metal organic frameworks at low temperature conditions: in situ infrared spectroscopy and Monte Carlo investigations

2021

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Nitrogen oxides (NOx) emissions from high temperature combustion processes under fuel-lean conditions continue to be a challenge for the energy industry. Selective catalytic reduction (SCR) has been possible with metal oxides and zeolites. There is still the need to identify catalytic materials that are efficient in reducing NOx to environmentally benign nitrogen gas at temperatures lower than 200°C. Metal-organic frameworks (MOFs) emerged as a class of highly porous materials with unique physical and chemical properties. This study is motivated by the lack of systematic investigations on SCR using MOFs under industrially-relevant conditions. Here, we investigate the extent of NO conversion with two commercially-available MOFs; Basolite F300 (Fe-BTC) and HKUST-1 (Cu-BTC), mixed with solid urea as a source for the reductant, ammonia gas. For comparison, experiments were also conducted using cobalt ferrite (CoFe2O4) as a non-porous counterpart to relate its reactivity to those obtained from MOFs. Fourier-transform infrared spectroscopy (FTIR) was utilized to identify gas and surface species the temperature range 115 -180°C. Computational analysis was performed using Monte Carlo (MC) simulations to quantify adsorption energies of different surface species. The results show that the rate of ammonia production from the in situ solid urea decomposition was higher using CoFe2O4 than Fe-BTC and Cu-BTC, and that there is very limited conversion of NO on the mixed solid urea-MOF systems due to site blocking. The main conclusions from this study is that MOFs have limited abilities in converting NO under low temperature conditions, and that surface regeneration requires additional experimental steps.

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

Cited by 5 publications

References 23 publications

Unbiased Quantification of the Electrochemical Stability Limits of Electrolytes and Ionic Liquids

Unbiased Quantification of the Electrochemical Stability Limits of Electrolytes and Ionic Liquids

NMR Study of the Reductive Decomposition of [BMIm][NTf₂] at Gold Electrodes and Indirect Electrochemical Conversion of CO₂

Mechanistic studies on the conversion of NO gas on urea-iron and copper metal organic frameworks at low temperature conditions: in situ infrared spectroscopy and Monte Carlo investigations

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

Cited by 5 publications

References 23 publications

Unbiased Quantification of the Electrochemical Stability Limits of Electrolytes and Ionic Liquids

Unbiased Quantification of the Electrochemical Stability Limits of Electrolytes and Ionic Liquids

NMR Study of the Reductive Decomposition of [BMIm][NTf2] at Gold Electrodes and Indirect Electrochemical Conversion of CO2

Mechanistic studies on the conversion of NO gas on urea-iron and copper metal organic frameworks at low temperature conditions: in situ infrared spectroscopy and Monte Carlo investigations

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NMR Study of the Reductive Decomposition of [BMIm][NTf₂] at Gold Electrodes and Indirect Electrochemical Conversion of CO₂