Do all ionic liquids need organic cations? Characterisation of [AlCl2·nAmide]+ AlCl4− and comparison with imidazolium based systems

Abood, Hadi M. A.; Abbott, Andrew P.; Ballantyne, Andrew D.; Ryder, Karl S.

doi:10.1039/c0cc04989a

Cited by 207 publications

(161 citation statements)

References 18 publications

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“…The FTIR examination of the solid material in the first case revealed only the existence of urea vibrational bands. This could be related to the changing in the mole ratio of ionic liquid state as some aluminum chloride was consumed in the Lewis acid-base reaction and forming a system out of the limitation of liquid state reported for this type of ionic liquid as being between 2:1 and 1:1 (AlCl3: amide) [3].However in the second case, this was not observed properly due to dissolution of calcium complex formed with urea making a new liquid system mixture with other species present. This needs to be confirmed by further work which was out of the scope of the present research.…”

Section: Fig(2) Uv/vis Spectra Of (A) Benzene and (B) Ionic Liquid mentioning

confidence: 99%

“…imidazolium chloridebutwith promising similar properties in at least to its catalytic behavior for organic reactions and aluminum metal coating on metal substrate [3]. AlCl3-amide ionic liquids reported to become colored upon dilution with some organic solvents and the color was attributed to charge transfer between solvents and aluminum cations.…”

Section: Introductionmentioning

confidence: 99%

“…Aluminum chloride-based ionic liquids with imidazolium orpyridinium chlorides (chloroaluminate ionic liquids) werethefirst studied ionic liquids. Chloroaluminate ionic liquid was reported to formbasic, neutral andacidic melts by varyingthe molar ratio of the organic salt to AlCl3 [3].Basic ionic liquids with a molar ratio ofAlCl3 of less than 1 consist of R + , Cl  andAlCl4  ions. A molar ratio of AlCl3:RCl greater than 1 formacidic ionic liquid which contains R + , Al2Cl7  and AlCl4  ions [3,4].Aluminum chloride with simple amide (urea or acetamide) forms acidic ionic liquid consisted of positive acidic species [AlCl2.nAmide] + and ionic species [AlCl4]  having comparable properties to those of chloroaluminate ionic liquid [3].…”

Section: Introductionmentioning

confidence: 99%

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Investigation of Lewis Acid-Base Reaction of Acidic Species Present in Aluminum Chloride-Urea Ionic Liquid [AlCl2.nUrea] +

Abood¹,

Fadhil²

2017

JNUS

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Aluminum chloride-urea ionic liquid was investigated for its active species concentration with the aide of electronic spectroscopy by Lewis acid-base titration with chloride ions. A coordination bonds between aluminum cationic species of the ionic liquid and the aromatic ring of toluene or benzene was assumed to be responsible for new formed bands in visible and ultraviolet regions. Upon Lewis acid-base titration these bands disappeared and the concentration of the acidic species were elucidated to be around 75 mole% of the initial aluminum chloride used to prepare a 1.5 mole aluminum chloride to 1 mole urea ionic liquid. The product of this reaction assumed to be between 1 acidic species to 1 chloride ion according to the mole fraction elucidated graph.

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Section: Fig(2) Uv/vis Spectra Of (A) Benzene and (B) Ionic Liquid mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Investigation of Lewis Acid-Base Reaction of Acidic Species Present in Aluminum Chloride-Urea Ionic Liquid [AlCl2.nUrea] +

Abood¹,

Fadhil²

2017

JNUS

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“…Here, a high Coulombic efficiency (∼99.7%) Al battery is developed using earth-abundant aluminum as the anode, graphite as the cathode, and a cheap ionic liquid analog electrolyte made from a mixture of AlCl 3 and urea in a 1.3:1 molar ratio. The battery displays discharge voltage plateaus around 1.9 and 1.5 V (average discharge = 1.73 V) and yielded a specific cathode capacity of ∼73 mAh g −1 at a current density of 100 mA g −1 (∼1.4 C).…”

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confidence: 99%

High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte

Angell

Pan

Rong

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

344

285

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In recent years, impressive advances in harvesting renewable energy have led to a pressing demand for the complimentary energy storage technology. Here, a high Coulombic efficiency (∼99.7%) Al battery is developed using earth-abundant aluminum as the anode, graphite as the cathode, and a cheap ionic liquid analog electrolyte made from a mixture of AlCl 3 and urea in a 1.3:1 molar ratio. The battery displays discharge voltage plateaus around 1.9 and 1.5 V (average discharge = 1.73 V) and yielded a specific cathode capacity of ∼73 mAh g −1 at a current density of 100 mA g −1 (∼1.4 C). High Coulombic efficiency over a range of charge-discharge rates and stability over ∼150-200 cycles was easily demonstrated. In situ Raman spectroscopy clearly showed chloroaluminate anion intercalation/deintercalation of graphite (positive electrode) during charge-discharge and suggested the formation of a stage 2 graphite intercalation compound when fully charged. + cations. This battery is a promising prospect for a future high-performance, low-cost energy storage device.aluminum-ion battery | urea electrolyte | ionicity | ionic liquid | energy storage C heap, high-rate (fast charge/discharge) rechargeable batteries with long cycle lives are urgently needed for grid-scale storage of renewable energy, as it is becoming increasingly important to replace fossil fuels (1). Lithium-ion batteries (LIBs) are expensive and have limited cycle life, which makes them nonideal for grid-scale energy storage. Furthermore, high-rate capability is necessary for use in the grid, under which conditions LIBs become increasingly unsafe due to the flammability of the electrolytes used. Batteries based on aluminum offer a viable alternative due to aluminum's three-electron redox properties (offers potential for high-capacity batteries), stability in the metallic state, and very high natural abundance. Furthermore, the development of these batteries based on nonflammable electrolytes of low toxicity is critical for minimizing safety hazard and environmental impact. Recently, our group developed a secondary Al battery system based on the reversible deposition/stripping of aluminum at the Al negative electrode and reversible intercalation/deintercalation of chloroaluminate anions at the graphite positive electrode in a nonflammable 1-ethyl-3-methylimidazolium chloroaluminate (EMIC-AlCl 3 ) IL electrolyte (7,8). A ratio of AlCl 3 /EMIC = 1.3 by mole was used such that Al 2 Cl 7 − was present in the (acidic) electrolyte to facilitate aluminum deposition (9). During charging, Al 2 Cl 7 − is reduced to deposit aluminum metal, and AlCl 4 − ions intercalate (to maintain neutrality) in graphite as carbon is oxidized. During discharge, this battery exhibited a cathode specific capacity of ∼70 mAh g −1 with a Coulombic efficiency (CE) of 97-98%, and ultrahigh charge/discharge rate (up to 5,000 mA g −1 ) for over 7,000 cycles. However, room for improvement exists as the parameter space for the Al battery remains largely unexplored. The three-electron redox properti...

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“…8,12 A subtype of DES are metal-based eutectics made from metal salts like ZnCl 2 , FeCl 3 , SnCl 2 , AlCl 3 , and simple organic alcohols or amides as HBDs. 13,14 The donor molecule serves as a complexing agent and coordinates to the cation.…”

Section: Carolin Rußmentioning

confidence: 99%

Low melting mixtures in organic synthesis – an alternative to ionic liquids?

2012

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Do all ionic liquids need organic cations? Characterisation of [AlCl2·nAmide]+ AlCl4− and comparison with imidazolium based systems

Cited by 207 publications

References 18 publications

Investigation of Lewis Acid-Base Reaction of Acidic Species Present in Aluminum Chloride-Urea Ionic Liquid [AlCl2.nUrea] +

Investigation of Lewis Acid-Base Reaction of Acidic Species Present in Aluminum Chloride-Urea Ionic Liquid [AlCl2.nUrea] +

High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte

Low melting mixtures in organic synthesis – an alternative to ionic liquids?

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Do all ionic liquids need organic cations? Characterisation of [AlCl2·nAmide]+ AlCl4− and comparison with imidazolium based systems

Cited by 207 publications

References 18 publications

Investigation of Lewis Acid-Base Reaction of Acidic Species Present in Aluminum Chloride-Urea Ionic Liquid [AlCl2.nUrea] +

Investigation of Lewis Acid-Base Reaction of Acidic Species Present in Aluminum Chloride-Urea Ionic Liquid [AlCl2.nUrea] +

High Coulombic efficiency aluminum-ion battery using an AlCl 3 -urea ionic liquid analog electrolyte

Low melting mixtures in organic synthesis – an alternative to ionic liquids?

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High Coulombic efficiency aluminum-ion battery using an AlCl ₃ -urea ionic liquid analog electrolyte