Spectroscopic investigation of aluminum trihalides-tetrahydrofuran complexes.  2.  Solutions of aluminum chloride or bromide in tetrahydrofuran and in (tetrahydrofuran-dichloromethane)

Derouault, J.; Granger, Pascal; Forel, Marie-Thérèse

doi:10.1021/ic50178a046

Cited by 66 publications

(52 citation statements)

References 6 publications

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“…We analyzed the relative concentrations of ions in the electrolyte, Al NMR spectroscopy and found Al species (23,24) consistent with chloroaluminate anions and a urea-coordinated cation in the electrolytes (Fig. 4 C and D).…”

Section: Resultsmentioning

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.

336

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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Section: Resultsmentioning

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.

336

285

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“…The clas sical spectrum in the liquid consists in a single, narrow line, the position of which is quantitatively determined by the weighted average of the frequencies of the ex changing species [9][10][11]. The existence of [A1C14]~ with tetrahedral symmetry has been evidenced in dif ferent studies on alkali or organic cation based systems, and the 27A1 chemical shift has been reported between 100 and 105 ppm [12][13][14][15][16][17]. This appears not so evident for [Al2Cl7r , the existence of which has been proposed from the NMR linewidth evolution with composition and not in terms of a well defined chemical shift [13,[17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

²⁷Al NMR Spectra of the RECl₃-AlCl₃ (RE = Y, La) Glasses and Melts

Zissi

Bessada

2001

Zeitschrift Für Naturforschung A

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27 AI NMR spectra of pure crystalline and molten A1C13 and of RECI3-AICI3 (RE = Y, La) glass form ing binary mixtures have been obtained. Compositions corresponding mainly to YC13/A1C13 = 1/3 and LaCiyAlC^ = 1/3.7 have been studied from the glassy and crystalline state up to the melt. The 27A1 spectra can be unambiguously assigned to four-coordinated Al-species, such as A12C16, 'A1C14', and 'A12C17\ The chemical shifts lie between 95 and 110 ppm, very well separated with the -1.6 ppm giv en by the 'A1C16' coordination in solid A1C13. From the temperature evolution of the 27Al NMR spec tra, a description for the dynamic behaviour of these systems is proposed.

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“…[12] The upfield-shifted, broader peaks were assigned to complexes where chlorides were replaced with neutral Odonor ligands: [AlCl 3 L], [AlCl 3 L 2 ], and [AlCl 2 L 2 ] + . [13] The spectrum for SUr-AlCl 3 (c AlCl 3 ¼0.50) contained a peak corresponding to [AlCl 4 ] À , and a broad, downfield shifted signal at d = 109.3 ppm, which after close examination revealed a well-marked shoulder at around d = 119 ppm. These were assigned to [AlCl 3 SUr] and [AlCl 2 SUr 2 ] + complexes, respectively; S-donors cause downfield shift of the 27 Al NMR signal.…”

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confidence: 99%

Liquid Coordination Complexes Formed by the Heterolytic Cleavage of Metal Halides

2013

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Liquids containing very high metal concentrations are of value for a number of applications: from electrochemistry and Lewis acidic catalysis through to metals refining and inorganic materials syntheses. In the ideal case, such liquids should have well-controlled and tunable metal coordination, leading to adjustable physical properties (i.e. viscosity modifiable from mobile liquid to glass). Some of these requirements have been met by concentrated aqueous or acetonitrile solutions, [1] molten metals/alloys, molten salts, [2] ionic liquids, [3] or deep eutectic solvents.[4] However, each approach has some drawbacks, such as high cost, solubility limits, corrosiveness, or limited control over the metal coordination environment; consequently, the ideal system remains elusive.Herein, we describe a synthetic route to liquid coordination complexes (LCCs, shown in Figure 1), identify the metal coordination environment referring to in such systems, and present LCCs as a promising addition to the metals in the liquid state toolbox.A large number of ligands were reported to induce asymmetric splitting of the "M 2 Cl 6 " unit, where M = Al III or Ga III , leading to the formation of an ionic compound of formula [MCl 2 L 2 ][MCl 4 ].[5] These were investigated primarily within two distinct disciplines, coordination chemistry and electrochemistry. The traditional methodology of a coordination chemist involves allowing a metal halide and ligand to react in a solvent, using excess or equimolar amount of ligand, followed by the isolation of a crystalline product, and its analysis by single-crystal X-ray diffraction. Hence, inevitably, the majority of reported products of asymmetric cleavage are crystalline solids. For example, Richard and Beavers [6]

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Spectroscopic investigation of aluminum trihalides-tetrahydrofuran complexes. 2. Solutions of aluminum chloride or bromide in tetrahydrofuran and in (tetrahydrofuran-dichloromethane)

Cited by 66 publications

References 6 publications

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

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

²⁷Al NMR Spectra of the RECl₃-AlCl₃ (RE = Y, La) Glasses and Melts

Liquid Coordination Complexes Formed by the Heterolytic Cleavage of Metal Halides

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Spectroscopic investigation of aluminum trihalides-tetrahydrofuran complexes. 2. Solutions of aluminum chloride or bromide in tetrahydrofuran and in (tetrahydrofuran-dichloromethane)

Cited by 66 publications

References 6 publications

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

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

27Al NMR Spectra of the RECl3-AlCl3 (RE = Y, La) Glasses and Melts

Liquid Coordination Complexes Formed by the Heterolytic Cleavage of Metal Halides

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

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

²⁷Al NMR Spectra of the RECl₃-AlCl₃ (RE = Y, La) Glasses and Melts